WO2014119699A1 - Composition et procédé permettant de lutter contre les animaux nuisibles - Google Patents

Composition et procédé permettant de lutter contre les animaux nuisibles Download PDF

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Publication number
WO2014119699A1
WO2014119699A1 PCT/JP2014/052178 JP2014052178W WO2014119699A1 WO 2014119699 A1 WO2014119699 A1 WO 2014119699A1 JP 2014052178 W JP2014052178 W JP 2014052178W WO 2014119699 A1 WO2014119699 A1 WO 2014119699A1
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group
formula
compound
reaction
atom
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PCT/JP2014/052178
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English (en)
Japanese (ja)
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千枝 清水
将司 亀崎
吉彦 野倉
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住友化学株式会社
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Priority to BR112015017733A priority Critical patent/BR112015017733A2/pt
Priority to JP2014559762A priority patent/JP6191626B2/ja
Priority to CN201480006602.6A priority patent/CN104955333A/zh
Priority to EP14745632.1A priority patent/EP2962565A1/fr
Priority to US14/764,283 priority patent/US9723835B2/en
Publication of WO2014119699A1 publication Critical patent/WO2014119699A1/fr

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • A01N37/30—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof containing the groups —CO—N< and, both being directly attached by their carbon atoms to the same carbon skeleton, e.g. H2N—NH—CO—C6H4—COOCH3; Thio-analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • A01N43/52—1,3-Diazoles; Hydrogenated 1,3-diazoles condensed with carbocyclic rings, e.g. benzimidazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system

Definitions

  • the present invention relates to a pest control composition and a pest control method.
  • Non-Patent Document 1 discloses many compounds as active ingredients of pest control compositions.
  • An object of the present invention is to provide a pest control composition having an excellent control effect against pests.
  • the present invention is as follows.
  • Item 1 A compound represented by the following formula (1), or an N-oxide thereof, A pest control composition containing 4-oxo-4-[(2-phenylethyl) amino] -butyric acid.
  • Group X C1-C6 alkoxy group optionally having one or more halogen atoms, C3-C6 cycloalkyl optionally having one or more halogen atoms or one or more C1-C3 alkyl groups A group consisting of a group, a cyano group, a hydroxy group and a halogen atom.
  • Group W C1-C6 alkoxy group optionally having one or more halogen atoms, C3-C6 cycloalkyl group optionally having one or more halogen atoms, hydroxy group, halogen atom and cyano group A group consisting of ] Item 2.
  • R 1 is a C1-C6 alkyl group optionally having one or more atoms or groups selected from group Y;
  • R 2 and R 4 are hydrogen atoms
  • R 3 is a C1-C3 alkyl group optionally having one or more halogen atoms, —C (OR 10 ) 3 , a halogen atom or a hydrogen atom
  • R 5 is a C1-C3 alkyl group optionally having one or more halogen atoms, —OR 10 , —S (O) m R 10 , —CO 2 R 10 , —SF 5 or a halogen atom
  • R 6 is —OR 10 , —NR 10 R 11 , —CO 2 R 10 , —C (O) NR 10 R 11 , —OC (O) R 10 , a cyano group, a halogen atom or a hydrogen atom
  • R 7 is one or
  • Item 2 The pest control composition according to Item 1, wherein the group Y is a compound consisting of a C3-C6 cycloalkyl group optionally having one or more halogen atoms and a halogen atom, or an N-oxide thereof.
  • group Y is a compound consisting of a C3-C6 cycloalkyl group optionally having one or more halogen atoms and a halogen atom, or an N-oxide thereof.
  • R 1 is a C1-C3 alkyl group optionally having one or more halogen atoms
  • R 2 and R 4 are hydrogen atoms
  • R 3 is a C1-C3 alkyl group optionally having one or more halogen atoms, —C (OR 10 ) 3 , a halogen atom or a hydrogen atom
  • R 5 is a C1-C3 alkyl group optionally having one or more halogen atoms, —OR 10 , —S (O) m R 10 or a halogen atom
  • R 6 is a cyano group, —NR 10 R 11 , a halogen atom or a hydrogen atom
  • R 7 is a C1-C6 alkyl group optionally having one or more halogen atoms
  • R 8 is —S (O) m R 10 , a cyano group, a halogen atom or a hydrogen
  • R 1 is an ethyl group
  • R 2 and R 4 are hydrogen atoms
  • R 3 is a C1-C3 alkyl group optionally having one or more halogen atoms, —C (OR 10 ) 3 , a halogen atom or a hydrogen atom
  • R 5 is a C1-C3 haloalkyl group, —OR 20 , —S (O) m R 20 or a halogen atom
  • R 6 is a cyano group, —NR 10 R 11 , a halogen atom or a hydrogen atom
  • R 7 is a C1-C6 alkyl group optionally having one or more halogen atoms
  • R 8 is —S (O) m R 10 , a cyano group, a halogen atom or a hydrogen atom
  • R 10 and R 11 are the same or different and each is a C1-C
  • Item 5 The compound represented by the formula (1), or an N-oxide thereof, In the formula (1), Item 5.
  • Item 6. The compound represented by the formula (1), or an N-oxide thereof, In the formula (1), Item 5.
  • Item 7. The compound represented by the formula (1), or an N-oxide thereof, In the formula (1), Item 5.
  • Item 8 The compound represented by the formula (1), or an N-oxide thereof, Item 2.
  • Formula (1-2): [Where: R 1a represents a C1-C3 alkyl group, A 2a represents a nitrogen atom or CR 8a- , R 3a represents a C1-C3 alkyl group which may have one or more halogen atoms, —C (OR 10a ) 3 , a halogen atom or a hydrogen atom, R 5a represents a C1-C3 haloalkyl group, —OR 20a , —S (O) m R 20a or a halogen atom, R 6a represents a cyano group, —NR 10a R 11a , a halogen atom or a hydrogen atom, R 7a represents a C1-C6 alkyl group optionally having one or more halogen
  • Item 9 The compound represented by the formula (1), or an N-oxide thereof, Item 2.
  • Formula (1-3): [Where: A 2b represents a nitrogen atom or CR 8b- , R 3b represents a C1-C3 alkyl group which may have one or more halogen atoms, —C (OR 10b ) 3 , a halogen atom or a hydrogen atom, R 5b represents a C1-C3 haloalkyl group, —OR 20b , —S (O) m R 20b or a halogen atom, R 8b represents —S (O) m R 10b , a cyano group, a halogen atom or a hydrogen atom; R 10b represents a C1-C3 alkyl group optionally having one or more halogen atoms, R 20b represents a C1-
  • Item 10 The compound represented by the formula (1-3), or an N-oxide thereof,
  • R 3b is a halogen atom or a hydrogen atom
  • R 5b is a C1-C3 perfluoroalkyl group
  • R 30b is a C1-C3 perfluoroalkyl group
  • Item 10 The pest control composition according to Item 9, wherein R 8b is a halogen atom or a hydrogen atom, or an N-oxide thereof.
  • Item 11 The compound represented by the formula (1), or an N-oxide thereof, Item 5.
  • Formula (1-4): [Where: A 2c represents a nitrogen atom or CR 8c- , R 3c represents a C1-C3 alkyl group which may have one or more halogen atoms, —C (OR 10c ) 3 , a halogen atom or a hydrogen atom, R 5c represents a C1-C3 haloalkyl group, —OR 20c , —S (O) m R 20c or a halogen atom, R 8c represents -S (O) m R 10c , a cyano group, a halogen atom or a hydrogen atom, R 10c represents a C1-C3 alkyl group optionally having one or more halogen atoms, R 20c represents a C1-C3 haloalkyl group, m independently represents 0, 1 or 2, and n represents 0, 1
  • Item 12 The compound represented by the formula (1-4), or an N-oxide thereof,
  • R 3c is a halogen atom or a hydrogen atom
  • R 5c is a C1-C3 perfluoroalkyl group
  • R 30c is a C1-C3 perfluoroalkyl group
  • Item 13 The pest control composition according to Item 11, wherein R 8c is a halogen atom or a hydrogen atom, or an N-oxide thereof.
  • the ratio of the content of the compound represented by the formula (1) and 4-oxo-4-[(2-phenylethyl) amino] -butyric acid is 100: 1 to 1: 100 by weight ratio 8.
  • Item 14 The ratio of the content of the compound represented by the formula (1) and 4-oxo-4-[(2-phenylethyl) amino] -butyric acid is 10: 1 to 1:10 by weight ratio 8.
  • Item 15 A term wherein the ratio of the content of the compound represented by the formula (1-2) and 4-oxo-4-[(2-phenylethyl) amino] -butyric acid is 100: 1 to 1: 100 by weight. 9.
  • Item 16 The ratio of the content of the compound represented by the formula (1-2) and 4-oxo-4-[(2-phenylethyl) amino] -butyric acid is 10: 1 to 1:10 by weight. 9. The pest control composition according to 8. Item 17. A term wherein the ratio of the content of the compound represented by the formula (1-3) and 4-oxo-4-[(2-phenylethyl) amino] -butyric acid is 100: 1 to 1: 100 by weight. The pest control composition according to 9 or 10. Item 18. A term wherein the ratio of the content of the compound represented by the formula (1-3) and 4-oxo-4-[(2-phenylethyl) amino] -butyric acid is 10: 1 to 1:10 by weight.
  • the pest control composition according to 9 or 10. Item 19. A term wherein the ratio of the content of the compound represented by the formula (1-4) and 4-oxo-4-[(2-phenylethyl) amino] -butyric acid is 100: 1 to 1: 100 by weight. The pest control composition according to 11 or 12. Item 20. A term wherein the ratio of the content of the compound represented by the formula (1-4) and 4-oxo-4-[(2-phenylethyl) amino] -butyric acid is 10: 1 to 1:10 by weight. The pest control composition according to 11 or 12. Item 21. Item 21. A method for controlling pests, comprising a step of applying an effective amount of the pest control composition according to any one of Items 1 to 20 to a plant, plant seeds, bulbs, or soil in which plants are grown.
  • the pest control composition of the present invention comprises a compound represented by the formula (1) (hereinafter sometimes referred to as the present condensed heterocyclic compound) and 4-oxo-4-[(2-phenylethyl) amino. ] -Butyric acid.
  • N-oxide is a compound in which one or more ring nitrogen atoms of one or more heterocyclic parts are oxidized.
  • the heterocyclic moiety that can form an N-oxide include a pyridine ring moiety.
  • the nitrogen atom in the pyridine ring shown in formula (1) can be N ⁇ O.
  • a 2 can be N ⁇ O.
  • the notation of the Ca—Cb alkyl group in the present specification represents a linear or branched hydrocarbon group having a carbon number of a to b
  • the notation of the Ca—Cb haloalkyl group represents a linear or branched hydrocarbon group having a carbon number of a to b in which one or more hydrogen atoms bonded to a carbon atom are substituted with a halogen atom, At this time, when having two or more halogen atoms, those halogen atoms may be the same or different from each other.
  • the notation of the Ca—Cb alkoxy group represents a linear or branched alkyl-O— group having a carbon number of a to b
  • the notation of Ca—Cb cycloalkyl group represents a cyclic saturated hydrocarbon group having a to b carbon atoms.
  • the expression “which may have one or more atoms or groups selected from group X” means that when it has two or more atoms or groups selected from group X, those The atoms or groups selected from group X may be the same as or different from each other.
  • the expression “which may have one or more atoms or groups selected from group W” has two or more atoms or groups selected from group W. The atoms or groups selected from group W may be the same as or different from each other.
  • the expression “may have one or more halogen atoms” means that when two or more halogen atoms are present, the halogen atoms may be the same as or different from each other. May be.
  • halogen atom means a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • the notation “C1-C6 alkyl group optionally having one or more atoms or groups selected from group X” is an atom wherein a hydrogen atom bonded to a carbon atom is selected from group X Or a linear or branched saturated hydrocarbon group having 1 to 6 carbon atoms, optionally substituted with a group, wherein two or more atoms or groups selected from group X are substituted If present, the atoms or groups selected from group X may be the same as or different from each other.
  • C1-C6 alkyl group optionally having one or more atoms or groups selected from group X include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec- Butyl, tert-butyl, pentyl, neopentyl, hexyl, methoxymethyl, ethoxymethyl, propyloxymethyl, isopropyloxymethyl, butyloxymethyl, sec-butyloxymethyl, tert-butyl Oxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-propyloxyethyl group, 2-isopropyloxyethyl group, 2-butyloxyethyl group, 2-sec-butyloxyethyl group, 2-tert- Butyloxyethyl group, trifluoromethyl group, trichloromethyl group, 2- Fluoroethyl
  • C1-C6 alkyl group optionally having one or more halogen atoms is the number of carbon atoms in which a hydrogen atom bonded to a carbon atom is optionally substituted with a halogen atom.
  • C1-C6 alkyl group optionally having one or more halogen atoms examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
  • a C1-C6 alkyl group which may have one or more halogen atoms such as a heptafluoroisopropyl group is exemplified, and each is selected within the range of the designated number of carbon atoms.
  • examples of the “C1-C6 alkyl group optionally having one or more atoms or groups selected from group W” include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group.
  • examples of the “C1-C6 alkoxy group optionally having one or more halogen atoms” include a methoxy group, a trifluoromethoxy group, an ethoxy group, and 2,2,2-trifluoroethoxy.
  • Examples of the “C3-C6 cycloalkyl group optionally having one or more halogen atoms” in the present condensed heterocyclic compound include a cyclopropyl group, a 2,2-difluorocyclopropyl group, and a 2,2-dichlorocyclo group.
  • Examples include propyl group, 2,2-dibromocyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group.
  • examples of the “C3-C6 cycloalkyl group optionally having one or more halogen atoms or one or more C1-C3 alkyl groups” include a cyclopropyl group and 1-methylcyclopropyl. Group, 2-methylcyclopropyl group, 1-fluorocyclopropyl group, 2,2-difluorocyclopropyl group, 2,2-dichlorocyclopropyl group, 2,2-dibromocyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl Groups.
  • C1-C3 haloalkyl group refers to a straight or branched chain having 1 to 3 carbon atoms in which one or more hydrogen atoms bonded to carbon atoms are substituted with halogen atoms.
  • a chain-like hydrocarbon group is represented, and when it has two or more halogen atoms, these halogen atoms may be the same or different from each other.
  • C1-C3 haloalkyl group examples include a fluoromethyl group, a chloromethyl group, a bromomethyl group, an iodomethyl group, a difluoromethyl group, a dichloromethyl group, a trifluoromethyl group, a chlorodifluoromethyl group, a bromodifluoromethyl group, and trichloromethyl.
  • examples of the “C1-C3 alkyl group” include a methyl group, an ethyl group, a propyl group, and an isopropyl group.
  • examples of the “C1-C3 perfluoroalkyl group” include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, and a heptafluoroisopropyl group.
  • Examples of the present condensed heterocyclic compound include the following compounds.
  • R 1 is a C1-C6 alkyl group optionally having one or more atoms or groups selected from group Y;
  • R 2 and R 4 are hydrogen atoms
  • R 3 is a C1-C3 alkyl group optionally having one or more halogen atoms, —C (OR 10 ) 3 , a halogen atom or a hydrogen atom
  • R 5 is a C1-C3 alkyl group optionally having one or more halogen atoms, —OR 10 , —S (O) m R 10 , —CO 2 R 10 , —SF 5 or a halogen atom
  • R 6 is —OR 10 , —NR 10 R 11 , —CO 2 R 10 , —C (O) NR 10 R 11 , —OC (O) R 10 , a cyano group, a halogen atom or a hydrogen atom
  • R 7 is one or more halogen atoms optionally C1-C6
  • R 1 is a C1-C3 alkyl group optionally having one or more halogen atoms
  • R 2 and R 4 are hydrogen atoms
  • R 3 is a C1-C3 alkyl group optionally having one or more halogen atoms, —C (OR 10 ) 3 , a halogen atom or a hydrogen atom
  • R 5 is a C1-C3 alkyl group optionally having one or more halogen atoms, —OR 10 , —S (O) m R 10 or a halogen atom
  • R 6 is a cyano group, —NR 10 R 11 , a halogen atom or a hydrogen atom
  • R 7 is a C1-C6 alkyl group optionally having one or more halogen atoms
  • R 8 is —S (O) m R 10 , a cyano group, a halogen atom or a hydrogen atom,
  • R 1 is an ethyl group
  • R 2 and R 4 are hydrogen atoms
  • R 3 is a C1-C3 alkyl group which may have one or more halogen atoms, —C (OR 10 ) 3 , a halogen atom or a hydrogen atom
  • R 5 is a C1-C3 haloalkyl group, —OR 20 , —S (O) m R 20 or a halogen atom
  • R 6 is a cyano group, —NR 10 R 11 , a halogen atom or a hydrogen atom
  • R 7 is a C1-C6 alkyl group optionally having one or more halogen atoms
  • R 8 is —S (O) m R 10 , a cyano group, a halogen atom or a hydrogen atom
  • R 10 and R 11 are the same or different and each is a C1-C3 alkyl group optionally having one or more halogen atom
  • a 1 is —NR 7 —;
  • R 1 is a C1-C6 alkyl group optionally having one or more atoms or groups selected from group Y;
  • R 2 and R 4 are hydrogen atoms,
  • R 3 is a C1-C3 alkyl group optionally having one or more halogen atoms, —C (OR 10 ) 3 , a halogen atom or a hydrogen atom,
  • R 5 is a C1-C3 alkyl group optionally having one or more halogen atoms, —OR 10 , —S (O) m R 10 , —CO 2 R 10 , —SF 5 or a halogen atom;
  • R 6 is —OR 10 , —NR 10 R 11 , —CO 2 R 10 , —C (O) NR 10 R 11 , —OC (O) R 10 , a cyano group, a halogen atom or a hydrogen atom;
  • R 7 is
  • a 1 is —NR 7 —;
  • R 1 is a C1-C3 alkyl group optionally having one or more halogen atoms
  • R 2 and R 4 are hydrogen atoms
  • R 3 is a C1-C3 alkyl group optionally having one or more halogen atoms, —C (OR 10 ) 3 , a halogen atom or a hydrogen atom
  • R 5 is a C1-C3 alkyl group optionally having one or more halogen atoms, —OR 10 , —S (O) m R 10 or a halogen atom
  • R 6 is a cyano group, —NR 10 R 11 , a halogen atom or a hydrogen atom
  • R 7 is a C1-C6 alkyl group optionally having one or more halogen atoms
  • R 8 is —S (O) m R 10 , a cyano group, a halogen atom or a hydrogen atom
  • a 1 is —NR 7 —;
  • R 1 is an ethyl group,
  • R 2 and R 4 are hydrogen atoms,
  • R 3 is a C1-C3 alkyl group which may have one or more halogen atoms, —C (OR 10 ) 3 , a halogen atom or a hydrogen atom,
  • R 5 is a C1-C3 haloalkyl group, —OR 20 , —S (O) m R 20 or a halogen atom;
  • R 6 is a cyano group, —NR 10 R 11 , a halogen atom or a hydrogen atom,
  • R 7 is a C1-C6 alkyl group optionally having one or more halogen atoms,
  • R 8 is —S (O) m R 10 , a cyano group, a halogen atom or a hydrogen atom
  • R 10 and R 11 are the same or different and are C1-C3
  • a 1 is an oxygen atom
  • R 1 is a C1-C6 alkyl group optionally having one or more atoms or groups selected from group Y
  • R 2 and R 4 are hydrogen atoms
  • R 3 is a C1-C3 alkyl group optionally having one or more halogen atoms, —C (OR 10 ) 3 , a halogen atom or a hydrogen atom
  • R 5 is a C1-C3 alkyl group optionally having one or more halogen atoms, —OR 10 , —S (O) m R 10 , —CO 2 R 10 , —SF 5 or a halogen atom
  • R 6 is —OR 10 , —NR 10 R 11 , —CO 2 R 10 , —C (O) NR 10 R 11 , —OC (O) R 10 , a cyano group, a halogen atom or a hydrogen atom
  • R 7 is one or more halogen atom
  • a 1 is an oxygen atom
  • R 1 is a C1-C3 alkyl group optionally having one or more halogen atoms
  • R 2 and R 4 are hydrogen atoms
  • R 3 is a C1-C3 alkyl group optionally having one or more halogen atoms, —C (OR 10 ) 3 , a halogen atom or a hydrogen atom
  • R 5 is a C1-C3 alkyl group optionally having one or more halogen atoms, —OR 10 , —S (O) m R 10 or a halogen atom
  • R 6 is a cyano group, —NR 10 R 11 , a halogen atom or a hydrogen atom
  • R 7 is a C1-C6 alkyl group optionally having one or more halogen atoms
  • R 8 is —S (O) m R 10 , a cyano group, a halogen atom or a hydrogen atom
  • a 1 is a sulfur atom
  • R 1 is an ethyl group
  • R 2 and R 4 are hydrogen atoms
  • R 3 is a C1-C3 alkyl group which may have one or more halogen atoms, —C (OR 10 ) 3 , a halogen atom or a hydrogen atom
  • R 5 is a C1-C3 haloalkyl group, —OR 20 , —S (O) m R 20 or a halogen atom
  • R 6 is a cyano group, —NR 10 R 11 , a halogen atom or a hydrogen atom
  • R 7 is a C1-C6 alkyl group optionally having one or more halogen atoms
  • R 8 is —S (O) m R 10 , a cyano group, a halogen atom or a hydrogen atom
  • R 10 and R 11 are the same or different and each is a C1-C3 alkyl group optional
  • a 1 is a sulfur atom, or an N-oxide thereof.
  • a 1 is a sulfur atom
  • R 1 is a C1-C6 alkyl group optionally having one or more atoms or groups selected from group Y
  • R 2 and R 4 are hydrogen atoms
  • R 3 is a C1-C3 alkyl group optionally having one or more halogen atoms, —C (OR 10 ) 3 , a halogen atom or a hydrogen atom
  • R 5 is a C1-C3 alkyl group optionally having one or more halogen atoms, —OR 10 , —S (O) m R 10 , —CO 2 R 10 , —SF 5 or a halogen atom
  • R 6 is —OR 10 , —NR 10 R 11 , —CO 2 R 10 , —C (O) NR 10 R 11 , —OC (O) R 10 , a cyano group, a halogen atom or a hydrogen atom
  • R 7 is one or more halogen
  • a 1 is a sulfur atom
  • R 1 is a C1-C3 alkyl group optionally having one or more halogen atoms
  • R 2 and R 4 are hydrogen atoms
  • R 3 is a C1-C3 alkyl group optionally having one or more halogen atoms, —C (OR 10 ) 3 , a halogen atom or a hydrogen atom
  • R 5 is a C1-C3 alkyl group optionally having one or more halogen atoms, —OR 10 , —S (O) m R 10 or a halogen atom
  • R 6 is a cyano group, —NR 10 R 11 , a halogen atom or a hydrogen atom
  • R 7 is a C1-C6 alkyl group optionally having one or more halogen atoms
  • R 8 is —S (O) m R 10 , a cyano group, a halogen atom or a hydrogen atom,
  • a 1 is a sulfur atom
  • R 1 is an ethyl group
  • R 2 and R 4 are hydrogen atoms
  • R 3 is a C1-C3 alkyl group which may have one or more halogen atoms, —C (OR 10 ) 3 , a halogen atom or a hydrogen atom
  • R 5 is a C1-C3 haloalkyl group, —OR 20 , —S (O) m R 20 or a halogen atom
  • R 6 is a cyano group, —NR 10 R 11 , a halogen atom or a hydrogen atom
  • R 7 is a C1-C6 alkyl group optionally having one or more halogen atoms
  • R 8 is —S (O) m R 10 , a cyano group, a halogen atom or a hydrogen atom
  • R 10 and R 11 are the same or different and are C1-C3 alkyl groups optionally having one
  • R 1a represents a C1-C3 alkyl group
  • R 3a represents a C1-C3 alkyl group which may have one or more halogen atoms, —C (OR 10a ) 3 , a halogen atom or a hydrogen atom
  • R 5a represents a C1-C3 haloalkyl group
  • —OR 20a , —S (O) m R 20a or a halogen atom
  • R 6a represents a cyano group, —NR 10a R 11a , a halogen atom or a hydrogen atom
  • R 7a represents a C1-C6 alkyl group optionally having one or more halogen atoms
  • R 8a represents —S (O) m R 10a , a cyano group, a halogen atom or a hydrogen atom
  • R 10a and R 11a are the same or different
  • R 3b represents a C1-C3 alkyl group which may have one or more halogen atoms, —C (OR 10b ) 3 , a halogen atom or a hydrogen atom
  • R 5b represents a C1-C3 haloalkyl group, —OR 20b , —S (O) m R 20b or a halogen atom
  • R 8b represents —S (O) m R 10b , a cyano group, a halogen atom or a hydrogen atom
  • R 10b represents a C1-C3 alkyl group optionally having one or more halogen atoms
  • R 20b represents a C1-C3 haloalkyl group
  • m independently represents 0, 1 or 2
  • n represents 0, 1 or 2. Or a N-oxide thereof.
  • R 3b is a halogen atom or a hydrogen atom
  • R 5b is a C1-C3 perfluoroalkyl group
  • R 30b is a C1-C3 perfluoroalkyl group
  • R 8b is a compound which is a halogen atom or a hydrogen atom, or an N-oxide thereof.
  • R 3c represents a C1-C3 alkyl group which may have one or more halogen atoms, —C (OR 10c ) 3 , a halogen atom or a hydrogen atom
  • R 5c represents a C1-C3 haloalkyl group
  • R 20c represents a C1-C3 haloalkyl group
  • R 20c represents a C1-C3 alkyl group optionally having one or more halogen atoms
  • R 20c represents a C1-C3 haloalkyl group
  • m independently represents 0, 1 or 2
  • n represents 0, 1 or 2. Or a N-oxide thereof.
  • R 3c is a halogen atom or a hydrogen atom
  • R 5c is a C1-C3 perfluoroalkyl group
  • R 30c is a C1-C3 perfluoroalkyl group
  • R 8c is a compound which is a halogen atom or a hydrogen atom, or an N-oxide thereof.
  • a 1 is —NR 7 —, and R 7 is a C1-C6 alkyl group optionally having one or more halogen atoms or a hydrogen atom, or an N-oxide thereof;
  • compounds wherein A 1 is —NR 7 — and R 7 is a methyl group, an ethyl group or a propyl group, or an N-oxide thereof;
  • compounds wherein A 1 is —NR 7 — and R 7 is a methyl group, or an N-oxide thereof;
  • compounds wherein A 1 is —NR 7 — and R 7 is a hydrogen atom, or an N-oxide thereof;
  • a 1 is an oxygen atom, and A 2 is ⁇ N ( ⁇ O) — (N-oxide);
  • a 1 is an oxygen atom, and A 2 is ⁇ CR 8 —, or an N-oxide thereof;
  • a 1 is an oxygen atom, and A 2 is ⁇ CH—, or an N-oxide thereof;
  • a 1 is a sulfur atom, and A 2 is ⁇ CR 8 —, or an N-oxide thereof;
  • R 1 is a C1-C6 alkyl group optionally having one or more halogen atoms or a C3-C6 cycloalkyl group optionally having one or more halogen atoms.
  • a compound wherein R 1 is a C1-C3 alkyl group optionally having one or more halogen atoms, or an N-oxide thereof;
  • a compound wherein R 1 is an ethyl group or a cyclopropylmethyl group, or an N-oxide thereof;
  • a compound wherein R 1 is a methyl group, or an N-oxide thereof;
  • a compound wherein R 1 is an ethyl group, or an N-oxide thereof;
  • a compound wherein R 1 is an ethyl group, or an N-oxide thereof;
  • R 3 is a C1-C6 alkyl group optionally having one or more atoms or groups selected from group X, a halogen atom or a hydrogen atom, or an N-oxide thereof;
  • R 3 may be a C1-C3 alkyl group optionally having one or more halogen atoms, a compound that is —C (OR 10 ) 3 , a halogen atom or a hydrogen atom, or an N-oxide thereof ;
  • a compound wherein R 3 is a C1-C3 alkyl group optionally having one or more halogen atoms, or an N-oxide thereof;
  • compounds wherein R 3 is —C (OR 10 ) 3 , or an N-oxide thereof;
  • R 3 is a trifluoromethyl group, or N-oxides thereof;
  • R 3 is a trimethoxymethyl group, or an N-oxide thereof;
  • R 2 and R 4 are both hydrogen atoms in formula (1), or an N-oxide thereof;
  • R 2 and R 4 are both hydrogen atoms, and R 3 may be a C1-C3 alkyl group optionally having one or more halogen atoms, —C (OR 10 ) 3 , halogen atoms or A compound which is a hydrogen atom, or an N-oxide thereof;
  • a compound in which R 2 and R 4 are both hydrogen atoms and R 3 is a hydrogen atom in formula (1), or an N-oxide thereof;
  • a compound in which R 2 and R 4 are both hydrogen atoms and R 3 is a trifluoromethyl group, or an N-oxide thereof;
  • a compound in which R 2 and R 4 are both hydrogen atoms and R 3 is a trimethoxymethyl group in formula (1), or an N-oxide thereof;
  • R 5 may have one or more halogen atoms, C 1 -C 3 alkyl group, —OR 10 , —S (O) m R 10 , —CO 2 R 10 , —SF 5 Or a compound which is a halogen atom, or an N-oxide thereof;
  • a C1-C3 alkyl group optionally having one or more halogen atoms, —OR 10 , —S (O) m R 10 or a compound which is a halogen atom, or an N-oxide thereof;
  • a compound in which R 5 is a C1-C3 haloalkyl group, a C1-C3 haloalkoxy group, a C1-C3 haloalkylsulfanyl group, a C1-C3 haloalkylsulfinyl group, a C1-C3 haloalkylsulfonyl group, or a
  • R 5 is a C1-C3 perfluoroalkyl group, or an N-oxide thereof;
  • compounds wherein R 5 is a C1-C3 perfluoroalkoxy group, or an N-oxide thereof;
  • compounds wherein R 5 is a C1-C3 perfluoroalkylsulfanyl group, a C1-C3 perfluoroalkylsulfinyl group or a C1-C3 perfluoroalkylsulfonyl group, or an N-oxide thereof;
  • R 5 is a halogen atom, or an N-oxide thereof;
  • R 5 is a trifluoromethyl group, —CF 2 CF 3 , —CF 2 CF 2 CF 3 , —CF (CF 3 ) 2 ,
  • R 6 is —OR 10 , —NR 10 R 11 , —CO 2 R 10 , —C (O) NR 10 R 11 , a cyano group, a halogen atom or a hydrogen atom, or N thereof -Oxides;
  • R 6 is a cyano group, —NR 10 R 11 , a halogen atom or a hydrogen atom, or an N-oxide thereof;
  • R 5 is a C1-C3 haloalkyl group, a C1-C3 haloalkoxy group, a C1-C3 haloalkylsulfanyl group, a C1-C3 haloalkylsulfinyl group, a C1-C3 haloalkylsulfonyl group, or a halogen
  • R 5 is a C1-C3 perfluoroalkyl group and R 6 is a hydrogen atom, or an N-oxide thereof;
  • R 5 is a C1-C3 perfluoroalkoxy group and R 6 is a hydrogen atom, or an N-oxide thereof;
  • R 5 is a C1-C3 perfluoroalkylsulfanyl group, a C1-C3 perfluoroalkylsulfinyl group or a C1-C3 perfluoroalkylsulfonyl group, and R 6 is a hydrogen atom, or N thereof -Oxides;
  • a 1 is —NR 7 —, R 7 is a methyl group, A 2 is a nitrogen atom, and R 1 is a C1-C3 alkyl group optionally having one or more halogen atoms, R 2 and R 4 are both hydrogen atoms, R 3 is a C1-C3 alkyl group optionally having one or more halogen atoms, —C (OR 10 ) 3 , a halogen atom or a hydrogen atom, R 5 is a C1-C3 perfluoroalkyl group, C1 -C3 perfluoroalkoxy group, a C1-C3 perfluoroalkyl alkylsulfanyl group, C1-C3 perfluoroalkyl alkylsulfinyl group, C1-C3 perfluoroalkyl sulfonyl group or a halogen atom, R 6 is hydrogen atom, or a N-oxide; In Formula (1), A 1
  • a C1-C3 alkyl group, R 2 and R 4 are both hydrogen atoms
  • R 3 may be a C1-C3 alkyl group optionally having one or more halogen atoms, —C (OR 10 3 is a halogen atom or a hydrogen atom
  • R 5 is a C1-C3 perfluoroalkyl group, a C1-C3 perfluoroalkoxy group, a C1-C3 perfluoroalkylsulfanyl group, a C1-C3 perfluoroalkylsulfinyl group, a C1- A compound (N-oxide) which is a C3 perfluoroalkylsulfonyl group or a halogen atom, and R 6 is a hydrogen atom;
  • a 1 is —NR 7 —
  • R 7 is a methyl group
  • a 2 is ⁇ CR 8 —
  • R 8 is a C1-C3 alkoxy group,
  • R 6 is Compound is a atom, or an N- oxide;
  • a 1 is an oxygen atom
  • a 2 is a nitrogen atom
  • R 1 is a C1-C3 alkyl group optionally having one or more halogen atoms
  • both R 2 and R 4 are hydrogen atoms.
  • R 3 is a C1-C3 alkyl group optionally having one or more halogen atoms, —C (OR 10 ) 3 , a halogen atom or a hydrogen atom, and R 5 is a C1-C3 perfluoroalkyl group.
  • a 1 is an oxygen atom
  • a 2 is ⁇ N ( ⁇ O) —
  • R 1 is a C1-C3 alkyl group optionally having one or more halogen atoms
  • R 2 and R 4 Are both hydrogen atoms
  • R 3 is a C1-C3 alkyl group optionally having one or more halogen atoms, —C (OR 10 ) 3 , a halogen atom or a hydrogen atom
  • R 5 is C1- A C3 perfluoroalkyl group, a C1-C3 per
  • a 1 is an oxygen atom
  • a 2 is ⁇ CR 8 —
  • R 8 is a C1-C3 alkoxy group, a C1-C3 alkylsulfanyl group, a halogen atom or a hydrogen atom
  • R 1 Is a C1-C3 alkyl group which may have one or more halogen atoms
  • R 2 and R 4 are both hydrogen atoms
  • R 3 may have one or more halogen atoms.
  • R 5 is C1-C3 perfluoroalkyl group, C1-C3 perfluoroalkoxy group, C1-C3 perfluoroalkyl alkylsulfanyl group, C1-C3 perfluoroalkyl alkylsulfinyl group, a C1-C3 perfluoroalkyl sulfonyl group or a halogen atom
  • R 6 is hydrogen atom, or Of N- oxide
  • R 6a is a hydrogen atom, or an N-oxide thereof;
  • a compound wherein R 5a is a trifluoromethyl group and R 6a is a hydrogen atom, or an N-oxide thereof;
  • compounds wherein R 5a is —CF 2 CF 3 and R 6a is a hydrogen atom, or an N-oxide thereof;
  • compounds wherein R 5a is —S (O) CF 3 and R 6a is a hydrogen atom, or an N-oxide thereof;
  • compounds wherein R 5a is —
  • a 2a is ⁇ N ( ⁇ O) —
  • R 1a is an ethyl group
  • R 3a is a hydrogen atom
  • R 5a is a C1-C3 perfluoroalkyl group, C1- C3 perfluoroalkoxy group, C1-C3 perfluoroalkylsulfanyl group, C1-C3 perfluoroalkylsulfinyl group, C1-C3 perfluoroalkylsulfonyl group or a halogen atom
  • R 6a is a hydrogen atom (N-oxide) );
  • R 5b is a trifluoromethyl group, or N-oxides thereof;
  • R 5b is —CF 2 CF 3 , or an N-oxide thereof;
  • compounds wherein R 5b is —SCF 3 or an N-oxide thereof;
  • compounds wherein R 5b is —S (O) CF 3 , or an N-oxide thereof;
  • compounds wherein R 5b is —S (O) 2 CF 3 , or an N-oxide thereof;
  • a 2b is a nitrogen atom
  • R 3b is a hydrogen atom
  • R 5b is a C1-C3 perfluoroalkyl group, a C1-C3 perfluoroalkoxy group, a C1-C3 perfluoro
  • a 2b is ⁇ N ( ⁇ O) —, R 3b is a hydrogen atom, R 5b is a C1-C3 perfluoroalkyl group, a C1-C3 perfluoroalkoxy group, C1- A compound (N-oxide) which is a C3 perfluoroalkylsulfanyl group, a C1-C3 perfluoroalkylsulfinyl group, a C1-C3 perfluoroalkylsulfonyl group or a halogen atom;
  • a 2b is ⁇ CR 8b —, R 8 is a C1-C3 alkoxy group, a C1-C3 alkylsulf
  • a 2b is a nitrogen atom
  • R 3b is a trifluoromethyl group
  • R 5b is a C1-C3 perfluoroalkyl group, a C1-C3 perfluoroalkoxy group, or a C1-C3 perfluoro group.
  • a 2b is ⁇ N ( ⁇ O) —, R 3b is a trifluoromethyl group, R 5b is a C1-C3 perfluoroalkyl group, a C1-C3 perfluoroalkoxy group,
  • a compound (N-oxide) which is a C1-C3 perfluoroalkylsulfanyl group, a C1-C3 perfluoroalkylsulfinyl group, a C1-C3 perfluoroalkylsulfonyl group or a halogen atom;
  • a 2b is ⁇ CR 8b —, R 8 is a C1-C3 alk
  • R 5b is a C1-C3 perfluoroalkyl group, a C1-C3 perfluoroalkoxy group, a C1-C3 perfluoroalkylsulfanyl group, a C1-C3 perfluoroalkylsulfinyl group, a C1-C3 perfluoroalkylsulfonyl group, or a halogen atom. Or a N-oxide thereof;
  • R 5c is a trifluoromethyl group, or an N-oxide thereof;
  • R 5c is —CF 2 CF 3 , or an N-oxide thereof;
  • R 5c is —SCF 3 , or an N-oxide thereof;
  • compounds wherein R 5c is —S (O) CF 3 , or an N-oxide thereof;
  • compounds wherein R 5c is —S (O) 2 CF 3 , or an N-oxide thereof;
  • a 2c is a nitrogen atom
  • R 3c is a hydrogen atom
  • R 5c is a C1-C3 perfluoroalkyl group, a C1-C3 perfluoroal
  • a 2c is ⁇ N ( ⁇ O) —, R 3c is a hydrogen atom, R 5c is a C1-C3 perfluoroalkyl group, a C1-C3 perfluoroalkoxy group, C1- A compound (N-oxide) which is a C3 perfluoroalkylsulfanyl group, a C1-C3 perfluoroalkylsulfinyl group, a C1-C3 perfluoroalkylsulfonyl group or a halogen atom;
  • a 2c is a nitrogen atom
  • R 3c is a trifluoromethyl group
  • R 5c is a C1-C3 perfluoroalkyl group, a C1-C3 perfluoroalkoxy group, or a C1-C3 perfluoro group.
  • a 2c is ⁇ N ( ⁇ O) —, R 3c is a trifluoromethyl group, R 5c is a C1-C3 perfluoroalkyl group, a C1-C3 perfluoroalkoxy group, A compound (N-oxide) which is a C1-C3 perfluoroalkylsulfanyl group, a C1-C3 perfluoroalkylsulfinyl group, a C1-C3 perfluoroalkylsulfonyl group or a halogen atom;
  • a 2c is ⁇ CR 8c —, R 8 is a C1-C3 alk
  • R 5c is a C1-C3 perfluoroalkyl group, a C1-C3 perfluoroalkoxy group, a C1-C3 perfluoroalkylsulfanyl group, a C1-C3 perfluoroalkylsulfinyl group, a C1-C3 perfluoroalkylsulfonyl group or a halogen atom Or a N-oxide thereof.
  • the present condensed heterocyclic compound and intermediate compound can be produced, for example, by the following (Production Method 1) to (Production Method 24).
  • the present condensed heterocyclic compound in which n is 1 or 2 in formula (1) can be produced by oxidizing the present condensed heterocyclic compound in which n is 0. [Wherein the symbols have the same meaning as in formula (1). ]
  • the present condensed heterocyclic compound (1-n1) in which n is 1 in the formula (1) is produced by oxidizing the condensed heterocyclic compound (1-n0) in which n is 0 using an oxidizing agent. Can do.
  • the reaction is usually performed in the presence of a solvent. Examples of the solvent used in the reaction include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, alcohols such as methanol and ethanol, acetic acid, water, and mixtures thereof.
  • the oxidizing agent used for the reaction examples include sodium periodate or m-chloroperbenzoic acid.
  • the oxidizing agent is usually used at a ratio of 1 to 3 mol with respect to 1 mol of the present condensed heterocyclic compound (1-n0).
  • the oxidizing agent is used at a ratio of 1 to 1.2 mol with respect to 1 mol of the present condensed heterocyclic compound (1-n0).
  • the reaction temperature of the reaction is usually in the range of ⁇ 20 to 80 ° C.
  • the reaction time is usually in the range of 0.1 to 12 hours.
  • the reaction mixture is extracted with an organic solvent, and the organic layer is washed with an aqueous solution of a reducing agent (for example, sodium sulfite, sodium thiosulfate) or an aqueous solution of a base (for example, sodium bicarbonate) as necessary, dried,
  • a reducing agent for example, sodium sulfite, sodium thiosulfate
  • a base for example, sodium bicarbonate
  • the present condensed heterocyclic compound (1-n2) in which n is 2 in formula (1) is produced by oxidizing the present condensed heterocyclic compound (1-n1) in which n is 1 using an oxidizing agent.
  • the reaction is usually performed in the presence of a solvent.
  • the solvent used in the reaction include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, alcohols such as methanol and ethanol, acetic acid, water, and mixtures thereof.
  • the oxidizing agent used in the reaction include m-chloroperbenzoic acid and aqueous hydrogen peroxide.
  • the oxidizing agent is usually used at a ratio of 1 to 4 mol with respect to 1 mol of the present condensed heterocyclic compound (1-n1).
  • the oxidizing agent is used in a ratio of 1 to 2 moles with respect to 1 mole of the present condensed heterocyclic compound (1-n1).
  • the reaction temperature of the reaction is usually in the range of ⁇ 20 to 120 ° C.
  • the reaction time is usually in the range of 0.1 to 12 hours.
  • the reaction mixture is extracted with an organic solvent, and the organic layer is washed with an aqueous solution of a reducing agent (for example, sodium sulfite, sodium thiosulfate) or an aqueous solution of a base (for example, sodium bicarbonate) as necessary, dried,
  • a reducing agent for example, sodium sulfite, sodium thiosulfate
  • a base for example, sodium bicarbonate
  • the present condensed heterocyclic compound (1-n2) in which n is 2 in the formula (1) is obtained by oxidizing the present condensed heterocyclic compound (1-n0) in which n is 0 using an oxidizing agent. It can be produced by a step reaction (one pot). The reaction is usually performed in the presence of a solvent.
  • the solvent used in the reaction include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, alcohols such as methanol and ethanol, acetic acid, water, and mixtures thereof.
  • the oxidizing agent used in the reaction include m-chloroperbenzoic acid and aqueous hydrogen peroxide.
  • the reaction can be carried out in the presence of a catalyst as necessary.
  • the catalyst used in the reaction examples include sodium tungstate.
  • the oxidizing agent is usually used in a proportion of 2 to 5 mol, and the catalyst is usually used in a proportion of 0.01 to 0.5 mol.
  • the oxidizing agent is used in a proportion of 2 to 3 mol, and the catalyst is usually used in a proportion of 0.01 to 0.5 mol with respect to 1 mol of the present condensed heterocyclic compound (1-n0).
  • the reaction temperature of the reaction is usually in the range of 0 to 120 ° C.
  • the reaction time is usually in the range of 0.1 to 12 hours.
  • the reaction mixture is extracted with an organic solvent, and the organic layer is washed with an aqueous solution of a reducing agent (for example, sodium sulfite, sodium thiosulfate) or an aqueous solution of a base (for example, sodium bicarbonate) as necessary, dried,
  • a reducing agent for example, sodium sulfite, sodium thiosulfate
  • a base for example, sodium bicarbonate
  • Examples of the solvent used in the reaction include 1,4-dioxane, diethyl ether, tetrahydrofuran (hereinafter sometimes referred to as THF), ethers such as tert-butyl methyl ether, dichloromethane, chloroform, carbon tetrachloride, Halogenated hydrocarbons such as 1,2-dichloroethane and chlorobenzene, aromatic hydrocarbons such as toluene, benzene and xylene, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile, N, N-dimethylformamide (Hereinafter, sometimes referred to as DMF), N-methylpyrrolidone (hereinafter, sometimes referred to as NMP), 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide (hereinafter, sometimes referred to as DMSO).
  • THF tetrahydrofuran
  • Aprotic polar solvents such as pyridine, quinoline, etc. Containing aromatic compounds and mixtures thereof.
  • the condensing agent used in the reaction include carbodiimides such as 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (hereinafter sometimes referred to as EDCI hydrochloride) and 1,3-dicyclohexylcarbodiimide. Is mentioned.
  • This reaction can also be performed by adding a catalyst as needed.
  • the catalyst used in the reaction include 1-hydroxybenzotriazole (hereinafter sometimes referred to as HOBt).
  • the intermediate compound (M2) is usually in a proportion of 0.5 to 2 mol, the condensing agent is usually in a proportion of 1 to 5 mol, and the catalyst is usually 0 in 1 mol of the intermediate compound (M1). Used in a ratio of 01 to 1 mol.
  • the reaction temperature of the reaction is usually in the range of 0 to 120 ° C.
  • the reaction time of the reaction is usually in the range of 0.1 to 24 hours.
  • the reaction mixture is poured into water and extracted with an organic solvent and the organic layer is concentrated; the reaction mixture is poured into water and the resulting solid is collected by filtration; or formed in the reaction mixture.
  • the intermediate compound (M3) can be isolated by collecting the resulting solid by filtration.
  • the isolated intermediate compound (M3) can be further purified by recrystallization, chromatography or the like.
  • the intermediate compound (M3) can be produced by reacting the intermediate compound (M1) with the intermediate compound (M18).
  • the reaction is usually performed in the presence of a solvent.
  • the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aliphatic hydrocarbons such as hexane, heptane, and octane, and aromatics such as toluene and xylene.
  • This reaction can also be performed by adding a base as necessary.
  • the base used in the reaction includes alkali metal carbonates such as sodium carbonate and potassium carbonate, tertiary amines such as triethylamine and N, N-diisopropylethylamine, and nitrogen-containing aromatic compounds such as pyridine and 4-dimethylaminopyridine. And the like.
  • the intermediate compound (M18) is usually used in a proportion of 1 to 3 mol, and the base is usually used in a proportion of 1 to 10 mol.
  • the reaction temperature of the reaction is usually in the range of ⁇ 20 to 100 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the intermediate compound (M3) can be isolated by performing post-treatment operations such as adding water to the reaction mixture, extracting with an organic solvent, and drying and concentrating the organic layer. it can.
  • the isolated intermediate compound (M3) can be further purified by chromatography, recrystallization and the like.
  • This condensed heterocyclic compound (1) can be produced by intramolecular condensation of the intermediate compound (M3).
  • the reaction is usually performed in the presence of a solvent.
  • the solvent used in the reaction include ethers such as 1,4-dioxane, diethyl ether, THF, tert-butyl methyl ether, and halogenated carbonization such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, and chlorobenzene.
  • Hydrogens aromatic hydrocarbons such as toluene, benzene and xylene, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile, DMF, NMP, 1,3-dimethyl-2-imidazolidinone, DMSO, etc.
  • Aprotic polar solvents nitrogen-containing aromatic compounds such as pyridine and quinoline, and mixtures thereof.
  • a condensing agent, an acid, a base, or a chlorinating agent can be used as necessary.
  • Examples of the condensing agent used in the reaction include acetic anhydride, trifluoroacetic anhydride, EDCI hydrochloride, a mixture of triphenylphosphine and base and carbon tetrachloride or carbon tetrabromide, triphenylphosphine and diethyl azodicarboxylate, etc. Examples thereof include a mixture of azo diesters.
  • Examples of the acid used in the reaction include sulfonic acids such as p-toluenesulfonic acid, carboxylic acids such as acetic acid, polyphosphoric acid, and the like.
  • Examples of the base used in the reaction include pyridine, picoline, 2,6-lutidine, 1,8-diazabicyclo [5.4.0] -7-undecene (hereinafter sometimes referred to as DBU), 1,5. -Nitrogen-containing heterocyclic compounds such as diazabicyclo [4.3.0] -5-nonene, tertiary amines such as triethylamine, N, N-diisopropylethylamine, tripotassium phosphate, potassium carbonate, sodium hydride, etc. An inorganic base is mentioned. Examples of the chlorinating agent used in the reaction include phosphorus oxychloride.
  • the ratio of the condensing agent is usually 1 to 5 mol, and when an acid is used, the acid is usually 0.1 mol to 5 mol.
  • the base is usually used in a proportion of 1 to 5 mol
  • the chlorinating agent is usually used in a proportion of 1 to 5 mol.
  • the reaction temperature of the reaction is usually in the range of 0 to 200 ° C.
  • the reaction time of the reaction is usually in the range of 0.1 to 24 hours.
  • the reaction mixture After completion of the reaction, the reaction mixture is poured into water and extracted with an organic solvent and the organic layer is concentrated; the reaction mixture is poured into water and the resulting solid is collected by filtration; or formed in the reaction mixture.
  • the condensed heterocyclic compound (1) can be isolated by collecting the obtained solid by filtration.
  • the isolated present condensed heterocyclic compound (1) can be further purified by recrystallization, chromatography or the like.
  • the present condensed heterocyclic compound (1) can be produced in a one-step reaction (one pot) by reacting the intermediate compound (M1) and the intermediate compound (M2) in the presence of a condensing agent.
  • the reaction is usually performed in the presence of a solvent.
  • the solvent used in the reaction include ethers such as 1,4-dioxane, diethyl ether, THF, and tert-butyl methyl ether, and halogenations such as dichloromethane, chloroform, carbon tetrachloride, 1,2-diethane, and chlorobenzene.
  • Hydrocarbons aromatic hydrocarbons such as toluene, benzene, xylene, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile, DMF, NMP, 1,3-dimethyl-2-imidazolidinone, DMSO And aprotic polar solvents such as nitrogen, nitrogen-containing aromatic compounds such as pyridine and quinoline, and mixtures thereof.
  • the condensing agent used in the reaction include carbodiimides such as EDCI hydrochloride and 1,3-dicyclohexylcarbodiimide. This reaction can also be performed by adding a catalyst as needed. Examples of the catalyst used in the reaction include 1-hydroxybenzotriazole.
  • the intermediate compound (M2) is usually in a proportion of 0.5 to 2 mol
  • the condensing agent is usually in a proportion of 1 to 5 mol
  • the catalyst is usually in an amount of 0.8. It is used at a ratio of 01 to 1 mol.
  • the reaction temperature of the reaction is usually in the range of 0 to 200 ° C.
  • the reaction time of the reaction is usually in the range of 0.1 to 24 hours.
  • the reaction mixture is poured into water and extracted with an organic solvent and the organic layer is concentrated; the reaction mixture is poured into water and the resulting solid is collected by filtration; or formed in the reaction mixture.
  • the condensed heterocyclic compound (1) can be isolated by collecting the obtained solid by filtration.
  • the isolated present condensed heterocyclic compound (1) can be further purified by recrystallization, chromatography or the like.
  • the present condensed heterocyclic compound (1) can be produced in a one-step reaction (one pot) by reacting the intermediate compound (M1) with the intermediate compound (M18).
  • the reaction is usually performed in the presence or absence of a solvent.
  • the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aliphatic hydrocarbons such as hexane, heptane, and octane, and aromatics such as toluene and xylene.
  • This reaction can also be performed by adding a base as necessary.
  • the base used in the reaction includes alkali metal carbonates such as sodium carbonate and potassium carbonate, tertiary amines such as triethylamine and N, N-diisopropylethylamine, and nitrogen-containing aromatic compounds such as pyridine and 4-dimethylaminopyridine. And the like.
  • the intermediate compound (M18) is usually used in a proportion of 1 to 3 mol, and the base is usually used in a proportion of 1 to 10 mol.
  • the reaction temperature of the reaction is usually in the range of 20 to 200 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the condensed heterocyclic compound (1) is isolated by performing post-treatment operations such as adding water to the reaction mixture, extracting with an organic solvent, and drying and concentrating the organic layer. be able to.
  • the isolated present condensed heterocyclic compound (1) can be further purified by chromatography, recrystallization and the like.
  • An intermediate compound (M14) is reacted with the intermediate compound (M2) or the intermediate compound (M18) to produce an intermediate compound (M14). Can be reacted to produce the present condensed heterocyclic compound (P20) in which A 1 is a sulfur atom and A 2 is a nitrogen atom in formula (1). [Wherein the symbols have the same meaning as in formula (1). ]
  • the intermediate compound (M14) can be produced by reacting the intermediate compound (M9) and the intermediate compound (M2) in the presence of a condensing agent. The reaction is usually performed in the presence or absence of a solvent.
  • solvent used in the reaction examples include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aliphatic hydrocarbons such as hexane, heptane, and octane, and aromatics such as toluene and xylene.
  • the condensing agent used in the reaction examples include EDCI hydrochloride, carbodiimides such as 1,3-dicyclohexylcarbodiimide, and BOP reagent.
  • the intermediate compound (M2) is usually used in a proportion of 1 to 3 mol and the condensing agent is usually used in a proportion of 1 to 5 mol with respect to 1 mol of the intermediate compound (M9).
  • the reaction temperature of the reaction is usually in the range of 0 to 200 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the intermediate compound (M14) can be isolated by performing post-treatment operations such as adding water to the reaction mixture, extracting with an organic solvent, and drying and concentrating the organic layer. it can.
  • the isolated intermediate compound (M14) can be further purified by chromatography, recrystallization and the like.
  • the intermediate compound (M14) can be produced by reacting the intermediate compound (M9) with the intermediate compound (M18).
  • the reaction is usually performed in the presence or absence of a solvent.
  • a base can be added as necessary.
  • the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aliphatic hydrocarbons such as hexane, heptane, and octane, and aromatics such as toluene and xylene.
  • Aromatic hydrocarbons such as chlorobenzene, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile, aprotic polar solvents such as DMF, NMP and DMSO, nitrogen-containing compounds such as pyridine and quinoline Aromatic compounds and mixtures thereof are mentioned.
  • the base used in the reaction includes alkali metal carbonates such as sodium carbonate and potassium carbonate, tertiary amines such as triethylamine and N, N-diisopropylethylamine, and nitrogen-containing aromatic compounds such as pyridine and 4-dimethylaminopyridine. And the like.
  • the intermediate compound (M18) is usually used in a proportion of 1 to 3 mol, and the base is usually used in a proportion of 1 to 5 mol.
  • the reaction temperature of the reaction is usually in the range of 0 to 200 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the intermediate compound (M14) can be isolated by performing post-treatment operations such as adding water to the reaction mixture, extracting with an organic solvent, and drying and concentrating the organic layer. it can.
  • the isolated intermediate compound (M14) can be further purified by chromatography, recrystallization and the like.
  • This condensed heterocyclic compound (P20) can be produced by reacting the intermediate compound (14) with a sulfurizing agent.
  • the reaction is performed in the presence or absence of a solvent.
  • the solvent used in the reaction include ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran, tert-butyl methyl ether, and diglyme, and halogens such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, and chlorobenzene.
  • hydrocarbons aromatic hydrocarbons such as toluene, benzene and xylene, nitriles such as acetonitrile, nitrogen-containing aromatic compounds such as pyridine, picoline, lutidine and quinoline, and mixtures thereof.
  • sulfurizing agent used in the reaction include nilin pentasulfide, Lawesson's reagent (2,4-bis- (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetan-2,4-disulfide), and the like. Can be mentioned.
  • the sulfurizing agent is usually used in a ratio of 1 mol to 3 mol with respect to 1 mol of the intermediate compound (M14).
  • the reaction temperature of the reaction is usually in the range of 0 ° C. to 200 ° C., and the reaction time is usually in the range of 1 to 24 hours.
  • the reaction mixture is poured into water and extracted with an organic solvent and the organic layer is concentrated; the reaction mixture is poured into water and the resulting solid is collected by filtration; or formed in the reaction mixture.
  • the condensed heterocyclic compound (P20) can be isolated by collecting the obtained solid by filtration.
  • the isolated present condensed heterocyclic compound (P20) can be further purified by recrystallization, chromatography or the like.
  • This condensed heterocyclic compound can be produced by reacting the intermediate compound (M1) and the intermediate compound (M4) in the presence of an oxidizing agent. [Wherein the symbols have the same meaning as in formula (1). ] The reaction is usually performed in the presence of a solvent.
  • Examples of the solvent used in the reaction include alcohols such as methanol and ethanol, ethers such as 1,4-dioxane, diethyl ether, THF and tert-butyl methyl ether, dichloromethane, chloroform, carbon tetrachloride, 1,2- Halogenated hydrocarbons such as dichloroethane and chlorobenzene, aromatic hydrocarbons such as toluene, benzene and xylene, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile, DMF, NMP, 1,3-dimethyl- Examples thereof include aprotic polar solvents such as 2-imidazolidinone and DMSO, nitrogen-containing aromatic compounds such as pyridine and quinoline, and mixtures thereof.
  • alcohols such as methanol and ethanol
  • ethers such as 1,4-dioxane, diethyl ether, THF and ter
  • the reaction can be carried out by adding an acid as necessary.
  • the acid used in the reaction include sulfonic acids such as p-toluenesulfonic acid, carboxylic acids such as acetic acid, polyphosphoric acid, and the like.
  • the reaction can be carried out by adding sulfite as necessary.
  • the sulfite used in the reaction include sulfites such as sodium bisulfite and sodium disulfite.
  • the oxidizing agent used in the reaction include oxygen, copper (II) chloride, DDQ and the like.
  • the intermediate compound (M4) is usually in a proportion of 1 to 2 mol
  • the acid is usually in a proportion of 0.1 to 2 mol
  • the sulfite is usually in a proportion of 1 to 1 mol of the intermediate compound (M1).
  • the proportion of 5 moles and the oxidizing agent are usually used in the proportion of 1 mole to 5 moles.
  • the reaction temperature of the reaction is usually in the range of 0 to 200 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the reaction mixture is poured into water and extracted with an organic solvent and the organic layer is concentrated; the reaction mixture is poured into water and the resulting solid is collected by filtration; or formed in the reaction mixture.
  • the condensed heterocyclic compound (1) can be isolated by collecting the obtained solid by filtration.
  • the isolated present condensed heterocyclic compound (1) can be further purified by recrystallization, chromatography or the like.
  • the present condensed heterocyclic compound (1) in which n is 0 in the formula (1) can be produced by reacting the intermediate compound (M6) and the compound (M7) in the presence of a base.
  • V 2 represents a halogen atom, and other symbols have the same meaning as in formula (1).
  • the reaction is usually performed in the presence of a solvent.
  • Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, nitriles such as acetonitrile, DMF, Examples include aprotic polar solvents such as NMP and DMSO, water, and mixtures thereof.
  • Examples of the base used in the reaction include alkali metal carbonates such as sodium carbonate and potassium carbonate, and alkali metal hydrides such as sodium hydride.
  • the compound (M7) is usually used in a proportion of 1 to 10 mol, and the base is usually used in a proportion of 1 to 10 mol.
  • the reaction temperature of the reaction is usually in the range of 0 to 150 ° C.
  • the reaction time of the reaction is usually in the range of 0.5 to 24 hours.
  • the condensed heterocyclic compound (1) in which n is 0 can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent and drying and concentration of the organic layer. it can.
  • the isolated condensed heterocyclic compound (1) in which n is 0 can be further purified by chromatography, recrystallization or the like.
  • V 2 is preferably a fluorine atom or a chlorine atom.
  • the intermediate compound (M20) is reacted with the intermediate compound (M19) or the intermediate compound (M39) to produce an intermediate compound (M20).
  • the intermediate compound (M6) can be produced by condensation with Here, the production of the intermediate compound (M20) and the condensation in the molecule occur almost simultaneously, and the production of the intermediate compound (M20) may not be confirmed. [Wherein V 2 represents a halogen atom, and other symbols have the same meaning as in formula (1). ]
  • An intermediate compound (M20) can be produced according to the production method 2 using the intermediate compound (M19) instead of the intermediate compound (M2).
  • the intermediate compound (M20) can be produced according to the production method 2, using the intermediate compound (M39) instead of the intermediate compound (M18).
  • the intermediate compound (M6) can be produced according to the production method 2 using the intermediate compound (M20) instead of the intermediate compound (M3). Further, the intermediate compound (M6) can be produced in a one-step reaction (one pot) according to the production method 2 using the intermediate compound (M19) instead of the intermediate compound (M2). In addition, the intermediate compound (M6) can be produced in a one-step reaction (one pot) according to the production method 2 using the intermediate compound (M39) instead of the intermediate compound (M2).
  • V 2 is preferably a fluorine atom or a chlorine atom.
  • the present condensed heterocyclic compound (1) in which n is 0 can be produced according to the production method 2. it can. Further, the intermediate compound (M20) is used in place of the intermediate compound (M6), and according to the method of production method 5, the present condensed heterocyclic compound (1) in which n is 0 is reacted in one step (one pot). It can also be manufactured.
  • V 2 is preferably a fluorine atom or a chlorine atom.
  • the intermediate compound (M8) or the intermediate compound (M8 ′) which is a disulfide thereof and the compound (M17) are present in the presence of a base. It can manufacture by making it react below.
  • L represents a leaving group such as a chlorine atom, a bromine atom, an iodine atom, a trifluoromethanesulfonyloxy group or a methanesulfonyloxy group, and other symbols have the same meanings as in the formula (1).
  • the reaction is usually performed in the presence of a solvent.
  • Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, nitriles such as acetonitrile, DMF, Examples include aprotic polar solvents such as NMP and DMSO, and mixtures thereof.
  • Examples of the base used in the reaction include alkali metal or alkaline earth metal hydrides such as sodium hydride, potassium hydride and calcium hydride, inorganic bases such as sodium carbonate and potassium carbonate, and organic bases such as triethylamine. Can be mentioned.
  • the intermediate compound (M8 ′) that is a disulfide is usually performed in the presence of a reducing agent.
  • a reducing agent examples include sodium hydroxymethanesulfinate (trade name Rongalite).
  • the compound (M17) is usually used in a proportion of 1 to 10 mol
  • the base is usually used in a proportion of 1 to 10 mol.
  • the ratio of the compound (M17) is usually 2 to 10 mol and the base is usually 2 to 10 with respect to 1 mol of the intermediate compound (M8 ′).
  • a mole ratio and a reducing agent are usually used in a ratio of 1 to 5 moles.
  • the reaction temperature of the reaction is usually in the range of 0 to 100 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the condensed heterocyclic compound (1) in which n is 0 can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent and drying and concentration of the organic layer. it can.
  • the isolated condensed heterocyclic compound (1) in which n is 0 can be further purified by chromatography, recrystallization or the like.
  • the solvent used in the reaction examples include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, nitriles such as acetonitrile, DMF, Examples include aprotic polar solvents such as NMP and DMSO, and mixtures thereof.
  • the compound (M17′-1) is usually used at a ratio of 1 to 2 mol with respect to 1 mol of the intermediate compound (M8 ′).
  • the compound (M17′-2) When the compound (M17′-2) is used, the compound (M17′-2) is usually used at a ratio of 1 to 2 mol with respect to 1 mol of the intermediate compound (M8 ′).
  • the reaction temperature of the reaction is usually in the range of -80 to 100 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the condensed heterocyclic compound (1) in which n is 0 can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent and drying and concentration of the organic layer. it can.
  • the isolated condensed heterocyclic compound (1) in which n is 0 can be further purified by chromatography, recrystallization or the like.
  • the intermediate compound (M8) can be produced by reacting the intermediate compound (M6) with a sulfurizing agent. Moreover, the intermediate compound (M8 ′), which is a disulfide thereof, can be produced by oxidizing the intermediate compound (M8). [Wherein V 2 represents a halogen atom, and other symbols have the same meaning as in formula (1). ]
  • the intermediate compound (M8) can be produced according to the production method 5 using sodium sulfide, sodium hydrogen sulfide, hydrogen sulfide or the like instead of the compound (M7).
  • V 2 is preferably a fluorine atom or a chlorine atom.
  • the intermediate compound (M8 ′) can be produced by reacting two molecules of the intermediate compound (M8) in the presence of an oxidizing agent.
  • the reaction is usually performed in the presence of a solvent.
  • the solvent used in the reaction include water, alcohols such as methanol and ethanol, THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, ethers such as 1,4-dioxane, and aromatic hydrocarbons such as toluene and xylene.
  • Nitriles such as acetonitrile, aprotic polar solvents such as DMF, NMP and DMSO, carboxylic acids such as acetic acid, and mixtures thereof.
  • the oxidizing agent used in the reaction examples include oxygen, iodine, aqueous hydrogen peroxide, and potassium ferricyanide.
  • the oxidizing agent is usually used at a ratio of 0.5 to 10 mol with respect to 1 mol of the intermediate compound (M8).
  • the reaction temperature of the reaction is usually in the range of 0 to 100 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the intermediate compound (M8 ′) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer.
  • the isolated intermediate compound (M8 ′) can be further purified by chromatography, recrystallization and the like.
  • Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, nitriles such as acetonitrile, DMF, Examples include aprotic polar solvents such as NMP and DMSO, and mixtures thereof.
  • Examples of the base used in the reaction include alkali metal or alkaline earth metal hydrides such as sodium hydride, potassium hydride and calcium hydride, inorganic bases such as sodium carbonate and potassium carbonate, and organic bases such as triethylamine. Is mentioned.
  • the compound (M10) is usually used in a proportion of 1 to 5 mol and the base is usually used in a proportion of 1 to 3 mol with respect to 1 mol of the present condensed heterocyclic compound (P2).
  • the reaction temperature of the reaction is usually in the range of 0 to 100 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the condensed heterocyclic compound (P3) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer.
  • the isolated present condensed heterocyclic compound (P3) can be further purified by chromatography, recrystallization and the like.
  • the intermediate compound (M2) can be produced by hydrolyzing the intermediate compound (M37). [Wherein the symbols have the same meaning as in formula (1). ]
  • the reaction is usually carried out using an aqueous acid solution as a solvent.
  • the acid used for the reaction include mineral acids such as hydrochloric acid, nitric acid, phosphoric acid and sulfuric acid, and carboxylic acids such as acetic acid and trifluoroacetic acid.
  • the reaction temperature of the reaction is usually in the range of 0 to 100 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the intermediate compound (M2) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer.
  • the isolated intermediate compound (M2) can be further purified by chromatography, recrystallization and the like.
  • hydrolyzing with a base the reaction is usually carried out in the presence of a solvent.
  • the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, alcohols such as methanol and ethanol, water, and mixtures thereof.
  • the base used for the reaction include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide.
  • the base is generally used at a ratio of 1 to 10 mol per 1 mol of the intermediate compound (M37).
  • the reaction temperature of the reaction is usually in the range of 0 to 120 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the intermediate solution (M2) is isolated by acidifying the reaction solution and then performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. Can do.
  • the isolated intermediate compound (M2) can be further purified by chromatography, recrystallization and the like.
  • Intermediate compound (M18) can be produced by reacting intermediate compound (M2) in the presence of a chlorinating agent. [Wherein the symbols have the same meaning as in formula (1). ] The reaction is usually performed in the presence of a solvent.
  • the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, and aliphatic halogens such as dichloromethane and chloroform. Hydrocarbons and mixtures thereof.
  • Examples of the chlorinating agent used in the reaction include thionyl chloride, oxalyl dichloride, phosphorus oxychloride and the like.
  • the chlorinating agent is usually used at a ratio of 1 to 5 mol with respect to 1 mol of the intermediate compound (M2).
  • the reaction temperature of the reaction is usually in the range of 0 to 100 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the intermediate compound (M18) can be isolated by removing the solvent.
  • Intermediate compound (M2), intermediate compound (M4) or intermediate compound (M37) are respectively intermediate compound (M19), intermediate compound (M22) or intermediate compound (M36) and compound (M7). Can be produced by oxidizing the compound obtained as necessary. [Wherein V 2 represents a halogen atom, and other symbols have the same meaning as in formula (1). ] An intermediate compound (M2) in which n is 0 can be produced according to the production method 5 using the intermediate compound (M19) instead of the intermediate compound (M6). An intermediate compound (M4) in which n is 0 can be produced according to the production method 5 using the intermediate compound (M22) instead of the intermediate compound (M6). By using the intermediate compound (M36) instead of the intermediate compound (M6), an intermediate compound (M37) in which n is 0 can be produced according to the method of Production Method 5.
  • an intermediate compound (wherein n is 1 or 2) is used in place of the present condensed heterocyclic compound (1) where n is 0, and n is 0. M2) can be manufactured.
  • an intermediate compound in which n is 1 or 2 is used instead of the present condensed heterocyclic compound (1) in which n is 0, and n is 0. M4) can be manufactured.
  • an intermediate compound in which n is 1 or 2 is used instead of the present condensed heterocyclic compound (1) in which n is 0 and n is 0. M37) can be manufactured.
  • V 2 is preferably a fluorine atom or a chlorine atom.
  • An intermediate compound (M30) can be produced by nitration of the intermediate compound (M29) or by reacting the intermediate compound (M33) with the compound (M28). By reducing the intermediate compound (M30) obtained here, an intermediate compound (M1) in which A1 is —NR 7 — in the formula (M1) can be produced. [Wherein the symbols have the same meaning as in formula (1). ]
  • Intermediate compound (M30) can be produced by reacting intermediate compound (M33) with compound (M28) in the presence of a base.
  • the reaction is usually performed in the presence of a solvent.
  • the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, nitriles such as acetonitrile, DMF, Examples include aprotic polar solvents such as NMP and DMSO, and mixtures thereof.
  • This reaction can also be performed by adding a base as necessary.
  • Examples of the base used in the reaction include alkali metal hydrides such as sodium hydride, alkali metal carbonates such as sodium carbonate and potassium carbonate, tertiary amines such as triethylamine and N, N-diisopropylethylamine, and pyridine, Examples thereof include nitrogen-containing aromatic compounds such as 4-dimethylaminopyridine.
  • the compound (M28) is usually used in a proportion of 1 to 10 mol
  • the base is usually used in a proportion of 0 to 10 mol.
  • the reaction temperature of the reaction is usually in the range of 0 to 150 ° C.
  • the reaction time of the reaction is usually in the range of 0.5 to 24 hours.
  • the intermediate compound (M30) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer.
  • the isolated intermediate compound (M30) can be further purified by chromatography, recrystallization and the like.
  • Intermediate compound (M30) can be produced by reacting intermediate compound (M29) in the presence of a nitrating agent.
  • the reaction is usually performed in the presence of a solvent.
  • the solvent used in the reaction include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, acetic acid, concentrated sulfuric acid, concentrated nitric acid, water, and mixtures thereof.
  • the nitrating agent used in the reaction include concentrated nitric acid.
  • the nitrating agent is usually used at a ratio of 1 to 3 moles relative to 1 mole of the intermediate compound (M29).
  • the reaction temperature of the reaction is usually in the range of ⁇ 10 to 100 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the intermediate compound (M30) can be isolated by performing post-treatment operations such as pouring the reaction mixture into water, extraction with an organic solvent, and drying and concentration of the organic layer. .
  • the isolated intermediate compound (M30) can be further purified by chromatography, recrystallization and the like.
  • R 7 is a hydrogen atom in the formula (M30)
  • an intermediate compound wherein R 7 is hydrogen atom (M30) used in place of the compound (P2) according to the method of Preparation 11,
  • a compound in which R 7 is other than a hydrogen atom can also be produced.
  • the intermediate compound (M1) in which A 1 is —NR 7 — can be produced by reacting the intermediate compound (M30) with hydrogen in the presence of a hydrogenation catalyst.
  • the reaction is usually performed in a hydrogen atmosphere at 1 to 100 atm, usually in the presence of a solvent.
  • the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, esters such as ethyl acetate and butyl acetate, alcohols such as methanol and ethanol, water And mixtures thereof.
  • the hydrogenation catalyst used in the reaction include transition metal compounds such as palladium carbon, palladium hydroxide, Raney nickel, and platinum oxide.
  • hydrogen is usually used in a proportion of 3 mol and a hydrogenation catalyst is usually used in a proportion of 0.001 to 0.5 mol with respect to 1 mol of the intermediate compound (M30).
  • This reaction can also be performed by adding an acid, a base or the like, if necessary.
  • the acid used for the reaction include acetic acid and hydrochloric acid
  • examples of the base used for the reaction include tertiary amines such as triethylamine, magnesium oxide and the like.
  • the reaction temperature of the reaction is usually in the range of ⁇ 20 to 100 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • an intermediate compound in which A1 is —NR 7 — is obtained by performing post-treatment operations such as filtration of the reaction mixture, extraction with an organic solvent as necessary, and drying and concentration of the organic layer ( M1) can be isolated.
  • the isolated intermediate compound (M1) in which A1 is —NR 7 — can be further purified by chromatography, recrystallization, and the like.
  • the intermediate compound (M30) is prepared by acetylating the intermediate compound (M29) to produce an intermediate compound (M29 ′) as shown below, and then nitration of the obtained intermediate compound (M29 ′). It can also be produced by producing an intermediate compound (M30 ′) and hydrolyzing the obtained intermediate compound (M30 ′). [Wherein the symbols have the same meaning as in formula (1). ]
  • the intermediate compound (M29 ′) can be produced by reacting the intermediate compound (M29) in the presence of an acylating agent. The reaction is usually performed in the presence of a solvent or using an acylating agent as a solvent.
  • Examples of the solvent used in the reaction include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, and aromatics such as toluene and xylene. Group hydrocarbons, nitriles such as acetonitrile, aprotic polar solvents such as DMF, NMP, DMSO and mixtures thereof.
  • Examples of the acylating agent used in the reaction include acetic anhydride and paraacetoxynitrobenzene. This reaction can also be performed by adding a base as necessary.
  • the base used in the reaction examples include tertiary amines such as triethylamine and N, N-diisopropylethylamine, and nitrogen-containing aromatic compounds such as pyridine and 4-dimethylaminopyridine.
  • the acylating agent is usually used in a proportion of 1 mol or more and the base is usually used in a proportion of 0.1 to 10 mol with respect to 1 mol of the intermediate compound (M29).
  • the reaction temperature of the reaction is usually in the range of 0 to 150 ° C.
  • the reaction time of the reaction is usually in the range of 0.5 to 24 hours.
  • the intermediate compound (M29 ′) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer.
  • the isolated intermediate compound (M29 ′) can be further purified by chromatography, recrystallization and the like.
  • an intermediate compound (M30 ') can be produced according to the production method 15 using the intermediate compound (M29').
  • Intermediate compound (M30) can be produced by hydrolyzing intermediate compound (M30 ') in the presence of an acid or a base.
  • the reaction When hydrolyzing with an acid, the reaction is usually carried out using an aqueous acid solution as a solvent.
  • the acid used in the reaction include mineral acids such as hydrochloric acid and sulfuric acid, and carboxylic acids such as acetic acid and trifluoroacetic acid.
  • the reaction temperature of the reaction is usually in the range of 0 to 100 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the intermediate compound (M30) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated intermediate compound (M30) can be further purified by chromatography, recrystallization and the like.
  • the reaction When hydrolyzing with a base, the reaction is usually carried out in the presence of a solvent.
  • a solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, alcohols such as methanol and ethanol, water, and mixtures thereof.
  • the base used in the reaction include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, hydrazine and the like.
  • the base is usually used at a ratio of 1 to 10 mol per 1 mol of the intermediate compound (M30 ′).
  • the reaction temperature of the reaction is usually in the range of 0 to 120 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the intermediate solution (M30) is isolated by performing post-treatment operations such as acidification of the reaction solution, extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. Can do.
  • the isolated intermediate compound (M30) can be further purified by chromatography, recrystallization and the like.
  • Examples of the solvent used in the reaction include water, acetic acid, 1,4-dioxane, diethyl ether, THF and other ethers, ethyl acetate, butyl acetate and other esters, dichloromethane, chloroform, carbon tetrachloride, 1,2- Examples thereof include halogenated hydrocarbons such as dichloroethane, nitriles such as acetonitrile, aprotic polar solvents such as DMF, NMP and DMSO, and mixtures thereof.
  • Examples of the brominating agent used in the reaction include N-bromosuccinimide and bromine.
  • the brominating agent is usually used in a proportion of 1 to 3 mol per 1 mol of the intermediate compound (M29).
  • the reaction temperature of the reaction is usually in the range of ⁇ 10 to 100 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.
  • the reaction mixture is poured into water and extracted with an organic solvent and the organic layer is concentrated; the reaction mixture is poured into water and the resulting solid is collected by filtration; or formed in the reaction mixture.
  • the intermediate compound (M35) can be isolated by collecting the resulting solid by filtration.
  • the isolated intermediate compound (M35) can be further purified by recrystallization, chromatography or the like.
  • the intermediate compound (M1) in which A 1 is —NR 7 — can be produced by reacting the intermediate compound (M35) with an aminating agent in the presence of a copper compound.
  • the reaction is usually performed in the presence of a solvent.
  • the solvent used in the reaction include water, alcohols such as methanol and ethanol, ethers such as 1,4-dioxane, diethyl ether and THF, esters such as ethyl acetate and butyl acetate, dichloromethane, chloroform and tetrachloride.
  • Carbon, halogenated hydrocarbons such as 1,2-dichloroethane, nitriles such as acetonitrile, aprotic polar solvents such as DMF, NMP and DMSO, nitrogen-containing aromatic compounds such as pyridine and quinoline, and mixtures thereof can be mentioned.
  • the aminating agent used in the reaction include ammonia, aqueous ammonia, and lithium amide.
  • the copper compound used in the reaction include copper, copper (I) iodide, copper (I) oxide, copper (II) oxide, acetylacetone copper (II), copper acetate (II), copper sulfate (II) and the like. Can be mentioned.
  • This reaction can also be performed by adding a ligand as necessary.
  • the ligand used in the reaction include acetylacetone, salen, phenanthroline, and the like.
  • This reaction can also be performed by adding a base as necessary.
  • the base used in the reaction include pyridine, picoline, 2,6-lutidine, DBU, nitrogen-containing heterocyclic compounds such as 1,5-diazabicyclo [4.3.0] -5-nonene, triethylamine, N, N -Inorganic bases such as tertiary amines such as diisopropylethylamine, tripotassium phosphate, potassium carbonate, cesium carbonate and sodium hydroxide.
  • the aminating agent is usually used in a proportion of 1 to 5 mol
  • the copper compound is usually used in a proportion of 0.02 to 0.5 mol
  • the ligand is usually used with respect to 1 mol of the intermediate compound (M35).
  • the base is used in a proportion of 0.02 to 2 mol, and the base is usually used in a proportion of 1 to 5 mol.
  • the reaction temperature of the reaction is usually in the range of 30 to 200 ° C., and the reaction time is usually in the range of 0.1 to 48 hours. After completion of the reaction, the reaction mixture is poured into water and extracted with an organic solvent and the organic layer is concentrated; the reaction mixture is poured into water and the resulting solid is collected by filtration; or formed in the reaction mixture.
  • an intermediate compound (M1) in which A1 is —NR 7 — can be isolated.
  • the isolated intermediate compound (M1) in which A1 is —NR 7 — can be further purified by recrystallization, chromatography or the like.
  • intermediate compound (M32) is prepared by nitration of intermediate compound (M31), intermediate compound (M32) thus obtained is reduced to obtain an intermediate in which A1 is an oxygen atom in formula (M1).
  • Body compound (M1) can be produced. [Wherein the symbols have the same meaning as in formula (1). ]
  • the intermediate compound (M32) can be produced according to the production method 15 using the intermediate compound (M31) instead of the intermediate compound (M29).
  • An intermediate compound (M1) in which A1 is an oxygen atom can be produced according to the production method 15 using the intermediate compound (M32) instead of the intermediate compound (M30).
  • an intermediate compound (M34) is produced by reacting the intermediate compound (M33) with a sulfurizing agent, and then the obtained intermediate compound (M34) is reacted with a reducing agent.
  • An intermediate compound (M1) in which A1 is a sulfur atom can be produced. [Wherein the symbols have the same meaning as in formula (1). ]
  • Intermediate compound (M34) can be produced by reacting intermediate compound (M33) with thiourea in the presence of a base. The reaction is usually performed in the presence of a solvent. Examples of the solvent used in the reaction include alcohols such as methanol and ethanol, water, and mixtures thereof.
  • Examples of the base used for the reaction include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide.
  • thiourea is usually used in a proportion of 0.5 to 3 mol and the base is usually used in a proportion of 1 to 10 mol.
  • the reaction temperature of the reaction is usually in the range of 0 to 100 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • an intermediate compound (M34) can be isolated by performing post-treatment operations such as addition of an acid to the reaction mixture, extraction with an organic solvent, and drying and concentration of the organic layer. .
  • the isolated intermediate compound (M34) can also be purified by chromatography, recrystallization and the like.
  • the intermediate compound (M1) in which A1 is a sulfur atom can be produced by reacting the intermediate compound (M34) with a reducing agent.
  • the reduction reaction can be performed, for example, in the presence of metal powder such as iron powder and zinc powder; acid such as hydrochloric acid and acetic acid; and water.
  • the reaction is usually performed in the presence of a solvent.
  • Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, esters such as ethyl acetate and butyl acetate, alcohols such as methanol and ethanol, Examples include aprotic polar solvents such as DMF, NMP, DMSO, and mixtures thereof.
  • Examples of the reducing agent used in the reaction include metal powders such as iron powder, zinc powder, and tin dichloride. In the reaction, metal powder is usually used at a ratio of 3 to 10 moles with respect to 1 mole of the intermediate compound (M34).
  • the reaction temperature of the reaction is usually in the range of 0 to 100 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the intermediate compound (M1) in which A1 is a sulfur atom is obtained by performing post-treatment operations such as adding water to the reaction mixture, extracting with an organic solvent, and drying and concentrating the organic layer. It can be isolated.
  • the isolated intermediate compound (M1) in which A1 is a sulfur atom can also be purified by chromatography, recrystallization, and the like.
  • Examples of the solvent used in the reaction include aromatic hydrocarbons such as toluene and xylene, aprotic polar solvents such as DMF, NMP, and DMSO, and mixtures thereof.
  • Examples of the copper compound used for the reaction include copper and copper (I) iodide.
  • the compound (M11) is usually in a proportion of 1 to 10 mol and the copper compound is usually in a proportion of 0.5 to 10 mol with respect to 1 mol of the condensed heterocyclic compound (P4).
  • the reaction temperature of the reaction is usually in the range of 100 to 200 ° C.
  • the reaction time is usually in the range of 0.5 to 48 hours.
  • the intermediate compound (M11 ′) When the intermediate compound (M11 ′) is used in the reaction, potassium fluoride may be added.
  • the compound (M11 ′) is usually 1 to 10 mol
  • the copper compound is usually 0.1 to 10 mol
  • the potassium fluoride is usually 0.1 to 1 mol of the fused heterocyclic compound (P4). It is used in a proportion of 5 moles, and the reaction temperature of the reaction is usually in the range of 0 to 150 ° C.
  • the reaction time is usually in the range of 0.5 to 48 hours.
  • the condensed heterocyclic compound (P7) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer.
  • the isolated condensed heterocyclic compound (P7) isolated can be further purified by chromatography, recrystallization and the like.
  • V 1 is preferably a bromine atom or an iodine atom.
  • Examples of the solvent used in the reaction include aromatic hydrocarbons such as toluene and xylene, aprotic polar solvents such as DMF, NMP, and DMSO, and mixtures thereof.
  • Examples of the thiolating agent used in the reaction include sodium sulfide, sodium sulfide nonahydrate, and thiourea.
  • Examples of the catalyst used in the reaction include copper (I) chloride, copper (I) bromide, and copper (I) iodide.
  • This reaction can also be performed by adding a ligand as necessary.
  • Examples of the ligand used in the reaction include acetylacetone, salen, phenanthroline, and the like. This reaction can also be performed in presence of a base as needed.
  • the base used in the reaction examples include inorganic bases such as potassium carbonate, cesium carbonate, and tripotassium phosphate, and organic bases such as triethylamine.
  • the ratio of the thiolating agent is usually 1 to 10 moles
  • the catalyst is usually 0.1 to 5 moles
  • the ligand is usually 0.1.
  • the base is used in a proportion of 1 to 5 mol and the base is usually used in a proportion of 1 to 2 mol.
  • the reaction temperature of the reaction is usually in the range of 50 to 200 ° C.
  • the reaction time of the reaction is usually in the range of 0.5 to 24 hours.
  • the condensed heterocyclic compound (P9) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer.
  • the isolated present condensed heterocyclic compound (P9) can be further purified by chromatography, recrystallization and the like.
  • V 1 is preferably a bromine atom or an iodine atom.
  • the reaction from the condensed heterocyclic compound (P9) to the intermediate compound (P9 ′) is likely to occur, and the intermediate compound (P9 ′) may be generated during the synthesis of the condensed heterocyclic compound (P9). is there.
  • the intermediate compound (P9 ′) can be produced by reacting the present condensed heterocyclic compound (P9) in the presence of an oxidizing agent.
  • the reaction is usually performed in the presence of a solvent.
  • the solvent used in the reaction include water, alcohols such as methanol and ethanol, THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, ethers such as 1,4-dioxane, and aromatic hydrocarbons such as toluene and xylene.
  • Nitriles such as acetonitrile, aprotic polar solvents such as DMF, NMP and DMSO, carboxylic acids such as acetic acid, and mixtures thereof.
  • the oxidizing agent used in the reaction examples include oxygen, iodine, hydrogen peroxide solution, potassium ferricyanide, and the like.
  • the oxidizing agent is usually used at a ratio of 0.5 to 10 mol with respect to 1 mol of the present condensed heterocyclic compound (P9).
  • the reaction temperature of the reaction is usually in the range of 0 to 100 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the intermediate compound (P9 ′) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer.
  • the isolated intermediate compound (P9 ′) can be further purified by chromatography, recrystallization and the like.
  • the condensed heterocyclic compound (P9) is produced by thioesterifying the condensed heterocyclic compound (P4) to produce an intermediate compound (P9-1), and then hydrolyzing the obtained intermediate compound (P9-1). Can be manufactured.
  • R 10 ′ represents any one of R 10 other than a hydrogen atom in Formula (1), and other symbols have the same meaning as in Formula (1).
  • the intermediate compound (P9-1) can be produced by reacting the present condensed heterocyclic compound (P4) in the presence of a thioesterification agent, a base and a catalyst. The reaction is usually performed in the presence of a solvent.
  • Examples of the solvent used in the reaction include aromatic hydrocarbons such as toluene and xylene, aprotic polar solvents such as DMF, NMP, and DMSO, and mixtures thereof.
  • Examples of the thioesterifying agent used in the reaction include thiobenzoic acid.
  • Examples of the catalyst used in the reaction include copper (I) chloride, copper (I) bromide, and copper (I) iodide. This reaction can also be performed by adding a ligand as necessary. Examples of the ligand used in the reaction include acetylacetone, salen, phenanthroline, and the like.
  • the base used in the reaction examples include inorganic bases such as potassium carbonate, cesium carbonate, and tripotassium phosphate, and organic bases such as triethylamine.
  • the ratio of the thioesterification agent is usually 1 to 10 moles
  • the catalyst is usually 0.1 to 5 moles
  • the ligand is usually 0.1.
  • the base is used in a proportion of 1 to 5 mol and the base is usually used in a proportion of 1 to 2 mol.
  • the reaction temperature of the reaction is usually in the range of 50 to 200 ° C.
  • the reaction time of the reaction is usually in the range of 0.5 to 24 hours.
  • the intermediate compound (P9-1) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer.
  • the isolated intermediate compound (P9-1) can be further purified by chromatography, recrystallization and the like.
  • V 1 is preferably a bromine atom or an iodine atom.
  • This condensed heterocyclic compound (P9) can be produced by hydrolyzing the intermediate compound (P9-1).
  • the reaction is usually carried out using an aqueous acid solution as a solvent.
  • the acid used for the reaction include mineral acids such as hydrochloric acid, nitric acid, phosphoric acid and sulfuric acid, and carboxylic acids such as acetic acid and trifluoroacetic acid.
  • the reaction temperature of the reaction is usually in the range of 0 to 100 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the condensed heterocyclic compound (P9) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer.
  • the isolated present condensed heterocyclic compound (P9) can be further purified by chromatography, recrystallization and the like.
  • the reaction is usually carried out in the presence of a solvent.
  • the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, alcohols such as methanol and ethanol, water, and mixtures thereof.
  • the base used for the reaction include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide.
  • the base is usually used at a ratio of 1 to 10 mol with respect to 1 mol of the intermediate compound (P9-1).
  • the reaction temperature of the reaction is usually in the range of 0 to 120 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the condensed heterocyclic compound (P9) is isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. can do.
  • the isolated present condensed heterocyclic compound (P9) can be further purified by chromatography, recrystallization and the like.
  • the reaction from the condensed heterocyclic compound (P9) to the intermediate compound (P9 ′) is likely to occur, and the intermediate compound (P9 ′) may be generated during the synthesis of the condensed heterocyclic compound (P9). is there.
  • R 10 ′ represents any one of R 10 other than R 10 in Formula (1)
  • L represents a chlorine atom, a bromine atom, an iodine atom, a trifluoromethanesulfonyloxy group, a methanesulfonyloxy group, or the like. It represents a leaving group, and other symbols have the same meaning as in formula (1).
  • the reaction is usually performed in the presence of a solvent.
  • Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, nitriles such as acetonitrile, DMF, Examples include aprotic polar solvents such as NMP and DMSO, and mixtures thereof.
  • Examples of the base used in the reaction include alkali metal or alkaline earth metal hydrides such as sodium hydride, potassium hydride and calcium hydride, inorganic bases such as sodium carbonate and potassium carbonate, and organic bases such as triethylamine. Can be mentioned.
  • an intermediate compound (P9 ′) that is a disulfide When an intermediate compound (P9 ′) that is a disulfide is used, it is usually carried out in the presence of a reducing agent.
  • a reducing agent used in the reaction include sodium hydroxymethanesulfinate (trade name Rongalite).
  • the compound (M13) In the reaction, with respect to 1 mole of the present condensed heterocyclic compound (P9), the compound (M13) is usually used at a ratio of 1 to 10 moles, and the base is usually used at a ratio of 1 to 10 moles.
  • the compound (M13) When the intermediate compound (P9 ′) that is a disulfide is used, the compound (M13) is usually 2 to 10 moles and the base is usually 2 to 10 moles with respect to 1 mole of the intermediate compound (P9 ′).
  • a mole ratio and a reducing agent are used in a ratio of 1 to 5 moles.
  • the reaction temperature of the reaction is usually in the range of 0 to 100 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the condensed heterocyclic compound (P10-m0) in which m is 0 is isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. be able to.
  • the isolated condensed heterocyclic compound (P10-m0) in which m is 0 can also be further purified by chromatography, recrystallization, and the like.
  • compounds in which R 10 ′ is C1-C6 perfluoroalkyl are intermediate compounds (P9 ′), perfluoroalkyl iodide, and reduction. It can manufacture by making an agent react. The reaction is usually performed in the presence of a solvent.
  • Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, nitriles such as acetonitrile, DMF, Examples include aprotic polar solvents such as NMP and DMSO, and mixtures thereof.
  • Examples of the reducing agent used in the reaction include tetrakis (dimethylamino) ethylene.
  • perfluoroalkyl iodide examples include trifluoromethane iodide, pentafluoroethane iodide, heptafluoro-2-iodopropane, and the like.
  • perfluoroalkyl iodide is usually used in a proportion of 2 to 10 mol and a reducing agent in a proportion of 1 to 5 mol per 1 mol of the intermediate compound (P9 ′).
  • the reaction temperature of the reaction is usually in the range of ⁇ 80 to 50 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the condensed heterocyclic compound (P10-m0) in which m is 0 is isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. be able to.
  • the isolated condensed heterocyclic compound (P10-m0) in which m is 0 can also be further purified by chromatography, recrystallization, and the like.
  • this condensed heterocyclic compound in which m is 1 or 2 is reacted with this condensed heterocyclic compound (P10-m0) in which m is 0 in the presence of an oxidizing agent.
  • the reaction is usually performed in the presence of a solvent.
  • the solvent used in the reaction include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, alcohols such as methanol and ethanol, acetic acid, water, and mixtures thereof.
  • the oxidizing agent used in the reaction include m-chloroperbenzoic acid or hydrogen peroxide water.
  • the reaction can be carried out in the presence of a catalyst as necessary.
  • Examples of the catalyst used in the reaction include sodium tungstate.
  • the amount of the oxidizing agent is usually 1 to 5 mol and the catalyst is usually 0.01 to 0.5 mol with respect to the present condensed heterocyclic compound (P10-m0) in which 1 mol of m is 0. Used in proportions.
  • the ratio of the oxidizing agent is usually 0.8 to 1.2 moles relative to the present condensed heterocyclic compound (P10-m0) in which 1 mole of m is 0.
  • Is usually used in a proportion of 0.05 to 0.2 mol, and in the case of producing a compound in which m is 2, with respect to the present condensed heterocyclic compound (P10-m0) in which 1 mol of m is 0,
  • the oxidizing agent is usually used in a proportion of 1.8 to 5 mol
  • the catalyst is usually used in a proportion of 0.05 to 0.2 mol.
  • the reaction temperature of the reaction is usually in the range of ⁇ 20 to 120 ° C.
  • the reaction time is usually in the range of 0.1 to 12 hours.
  • the reaction mixture is extracted with an organic solvent, and the organic layer is washed with an aqueous solution of a reducing agent (for example, sodium sulfite, sodium thiosulfate) or an aqueous solution of a base (for example, sodium bicarbonate) as necessary, dried,
  • a reducing agent for example, sodium sulfite, sodium thiosulfate
  • a base for example, sodium bicarbonate
  • the present condensed heterocyclic compound (P11) in which R5 is —OH in the formula (1) can be produced from the present condensed heterocyclic compound (P4) via an intermediate compound (P11 ′).
  • V 1 represents a halogen atom, and other symbols have the same meaning as in formula (1).
  • the intermediate compound (P11 ′) can be produced by reacting the present condensed heterocyclic compound (P4) with benzyl alcohol in the presence of a base. The reaction is usually performed in the presence of a solvent or benzyl alcohol as a solvent.
  • Examples of the solvent used in the reaction include aromatic hydrocarbons such as toluene and xylene, aprotic polar solvents such as DMF, NMP, and DMSO, and mixtures thereof.
  • This reaction can also be performed by adding a catalyst as needed.
  • Examples of the catalyst used in the reaction include copper (I) chloride, copper (I) bromide, and copper (I) iodide.
  • This reaction can also be performed by adding a ligand as necessary. Examples of the ligand used in the reaction include acetylacetone, salen, phenanthroline, and the like. The reaction is usually performed in the presence of a base.
  • Examples of the base used in the reaction include inorganic bases such as potassium carbonate, cesium carbonate, and tripotassium phosphate.
  • benzyl alcohol is usually in a proportion of 1 to 10 mol
  • catalyst is usually in a proportion of 0.1 to 5 mol
  • ligand is usually in a proportion of 0.1 mol per mol of the condensed heterocyclic compound (P4).
  • the base is used in a proportion of ⁇ 5 mol, and the base is usually used in a proportion of 1 mol to 2 mol.
  • the reaction temperature of the reaction is usually in the range of 50 to 200 ° C.
  • the reaction time of the reaction is usually in the range of 0.5 to 24 hours.
  • the intermediate compound (P11 ′) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer.
  • the isolated intermediate compound (P11 ′) can be further purified by chromatography, recrystallization and the like.
  • V 1 is preferably a bromine atom or an iodine atom.
  • This condensed heterocyclic compound (P11) can be produced by reacting the intermediate compound (P11 ′) with hydrogen in the presence of a hydrogenation catalyst.
  • the reaction is usually performed in a hydrogen atmosphere at 1 to 100 atm, usually in the presence of a solvent.
  • the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, esters such as ethyl acetate and butyl acetate, alcohols such as methanol and ethanol, water And mixtures thereof.
  • the hydrogenation catalyst used in the reaction include transition metal compounds such as palladium carbon, palladium hydroxide, Raney nickel, and platinum oxide.
  • hydrogen is usually used in a proportion of 3 mol and a hydrogenation catalyst is usually used in a proportion of 0.001 to 0.5 mol with respect to 1 mol of the intermediate compound (P11 ′).
  • This reaction can also be performed by adding an acid, a base or the like, if necessary.
  • the acid used for the reaction include acetic acid and hydrochloric acid
  • examples of the base used for the reaction include tertiary amines such as triethylamine, magnesium oxide and the like.
  • the reaction temperature of the reaction is usually in the range of ⁇ 20 to 100 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the condensed heterocyclic compound (P11) is isolated by performing post-treatment operations such as filtration of the reaction mixture, extraction with an organic solvent as necessary, and drying and concentration of the organic layer. be able to.
  • the isolated present condensed heterocyclic compound (P11) can be further purified by chromatography, recrystallization or the like.
  • the condensed heterocyclic compound (P12) in which R 5 is —OR 10 ′ in the formula (1) can be produced by reacting the condensed heterocyclic compound (P11) and the compound (M13).
  • R 10 ′ represents any one of R 10 other than a hydrogen atom in Formula (1), and other symbols have the same meaning as in Formula (1).
  • the reaction is usually performed in the presence of a solvent.
  • Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, nitriles such as acetonitrile, DMF, Examples include aprotic polar solvents such as NMP and DMSO, and mixtures thereof.
  • Examples of the base used in the reaction include alkali metal or alkaline earth metal hydrides such as sodium hydride, potassium hydride and calcium hydride, inorganic bases such as sodium carbonate and potassium carbonate, and organic bases such as triethylamine. Can be mentioned.
  • the compound (M13) is usually used in a proportion of 1 to 10 mol, and the base is usually used in a proportion of 1 to 10 mol.
  • the reaction temperature of the reaction is usually in the range of 0 to 100 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the condensed heterocyclic compound (P12) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer.
  • the isolated present condensed heterocyclic compound (P12) can be further purified by chromatography, recrystallization or the like.
  • this condensed heterocyclic compound (P12) whose R ⁇ 10 ' > is a trifluoromethyl group among this condensed heterocyclic compounds (P12) can be manufactured with the following manufacturing methods. [Wherein the symbols have the same meaning as in formula (1). ]
  • the intermediate compound (P11 ′) can be produced by reacting the present condensed heterocyclic compound (P11) with a base, carbon disulfide and a methylating agent. The reaction is performed in the presence of a solvent.
  • the solvent used in the reaction include aprotic polar solvents such as DMF, NMP, and DMSO.
  • the base used for the reaction include alkali metal hydrides such as sodium hydride.
  • methyl iodide is mentioned, for example.
  • the base is usually in a proportion of 1 to 2 mol
  • the carbon disulfide is usually in a proportion of 1 to 10 mol
  • the methylating agent is usually in a proportion of 1 to 10 mol. It is used in the ratio.
  • the reaction temperature of the reaction is usually in the range of 0 to 100 ° C.
  • the reaction time of the reaction is usually in the range of 0.5 to 24 hours.
  • the intermediate compound (P11 ′) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer.
  • the isolated intermediate compound (P11 ′) can be further purified by chromatography, recrystallization and the like.
  • the condensed heterocyclic compound (P12) in which R 10 ′ is a trifluoromethyl group reacts the intermediate compound (P11 ′) with a fluorinating agent in the presence of a base.
  • a fluorinating agent in the presence of a base.
  • the reaction is performed in the presence of a solvent.
  • the solvent used in the reaction include halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, and 1,2-dichloroethane.
  • the reaction is carried out in the presence of a base and a fluorinating agent.
  • Examples of the base used in the reaction include 1,3-dibromo-5,5-dimethylhydantoin.
  • Examples of the fluorinating agent used in the reaction include tetra-n-butylammonium fluoride and a hydrogen fluoride pyridine complex.
  • the base is usually used at a ratio of 1 to 10 mol
  • the fluorinating agent is usually used at a ratio of 1 to 10 mol.
  • the reaction temperature of the reaction is usually in the range of ⁇ 80 to 50 ° C.
  • the reaction time of the reaction is usually in the range of 0.5 to 24 hours.
  • the condensed heterocyclic compound (P12) in which R 10 ′ is a trifluoromethyl group is obtained by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, drying of the organic layer, and concentration. It can be isolated.
  • the isolated condensed heterocyclic compound (P12) in which the isolated R 10 ′ is a trifluoromethyl group can be further purified by chromatography, recrystallization, and the like.
  • reaction method 24 Of the condensed heterocyclic compound and the intermediate compound described above, by reacting a compound having a nitrogen-containing heterocyclic moiety having a lone pair on the nitrogen atom with an oxidizing agent, the nitrogen atom may be oxidized in some cases. N-oxide can be produced. Examples of the nitrogen-containing heterocyclic moiety include a pyridine ring.
  • the reaction can be carried out by a known method, for example, in a solvent such as halogenated hydrocarbons such as dichloromethane, chloroform and chlorobenzene, alcohols such as methanol and ethanol, acetic acid, water and a mixture thereof. It is carried out using an oxidizing agent such as chloroperbenzoic acid or hydrogen peroxide.
  • 4-oxo-4-[(2-phenylethyl) amino] -butyric acid is a compound described in, for example, International Publication No. 99/45774 pamphlet, and can be produced by the methods described therein.
  • 4-Oxo-4-[(2-phenylethyl) amino] -butyric acid may be contained in the pest control composition of the present invention in the form of a salt.
  • salts include alkali metal salts such as sodium salt and potassium salt, alkaline earth metal salts such as calcium salt and magnesium salt, inorganic base salts such as ammonium, morpholine, piperidine, pyrrolidine, mono-alkylamine, di- Examples thereof include salts such as organic base salts such as organic amine salts such as alkylamine, tri-alkylamine, mono-hydroxyalkylamine, di-hydroxyalkylamine, and tri-hydroxyalkylamine.
  • the pest control composition of the present invention may be a simple mixture of the present condensed heterocyclic compound and 4-oxo-4-[(2-phenylethyl) amino] -butyric acid.
  • the compound, 4-oxo-4-[(2-phenylethyl) amino] -butyric acid and an inert carrier are mixed, and if necessary, a surfactant or other formulation adjuvant is added to obtain an oil or emulsion.
  • Flowable powders, wettable powders, granular wettable powders, powders, granules and the like are used.
  • the formulated pest control composition can be used as a pest control agent as it is or by adding other inactive components.
  • the total amount of the present condensed heterocyclic compound and 4-oxo-4-[(2-phenylethyl) amino] -butyric acid in the pest control composition of the present invention is usually 0.1% to 100% by weight, preferably The range is 0.2 to 90% by weight, more preferably 1 to 80% by weight.
  • examples of the inert carrier used for formulation include a solid carrier and a liquid carrier.
  • examples of the solid support include clays (kaolin clay, diatomaceous earth, bentonite, fusami clay, acidic clay), synthetic hydrous silicon oxide, talc, ceramic, and other inorganic minerals (sericite, quartz, sulfur, activated carbon, calcium carbonate).
  • polyester resin such as nylon-6, nylon-11, nylon-66, polyamide resin, polyvinyl chloride, polyvinylidene chloride, vinyl chloride-propylene copolymer).
  • liquid carrier examples include water, alcohols (methanol, ethanol, isopropyl alcohol, butanol, hexanol, benzyl alcohol, ethylene glycol, propylene glycol, phenoxyethanol, etc.), ketones (acetone, methyl ethyl ketone, cyclohexanone, etc.), aromatic hydrocarbons (Toluene, xylene, ethylbenzene, dodecylbenzene, phenylxylylethane, methylnaphthalene, etc.), aliphatic hydrocarbons (hexane, cyclohexane, kerosene, light oil, etc.), esters (ethyl acetate, butyl acetate, isopropyl myristate, Ethyl oleate, diisopropyl adipate, diisobutyl adipate, propylene glycol monomethyl ether acetate, etc.), n
  • Acid amides N, N-dimethylformamide, N, N-dimethylacetamide, etc.
  • halogenated hydrocarbons diichloromethane, trichloroethane, carbon tetrachloride, etc.
  • sulfoxides dimethylsulfoxide, etc.
  • propylene carbonate and vegetable oil Soybean oil, cottonseed oil, etc.
  • surfactant examples include nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, and polyethylene glycol fatty acid ester, and negative ions such as alkyl sulfonate, alkyl benzene sulfonate, and alkyl sulfate.
  • nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, and polyethylene glycol fatty acid ester
  • negative ions such as alkyl sulfonate, alkyl benzene sulfonate, and alkyl sulfate.
  • An ionic surfactant is mentioned.
  • adjuvants for preparation include fixing agents, dispersants, colorants and stabilizers, such as casein, gelatin, saccharides (starch, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite, Synthetic water-soluble polymers (polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acids, etc.), PAP (isopropyl acid phosphate), BHT (2,6-di-tert-butyl-4-methylphenol), BHA (2-tert- And a mixture of butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol).
  • fixing agents such as casein, gelatin, saccharides (starch, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite, Synthetic water-soluble polymers (polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acids, etc.), PAP (is
  • the content ratio of the present condensed heterocyclic compound and 4-oxo-4-[(2-phenylethyl) amino] -butyric acid in the pest control composition of the present invention is not particularly limited, 4-Oxo-4-[(2-phenylethyl) amino] -butyric acid is usually 10 to 100,000 parts by weight, preferably 100 to 10,000 parts by weight with respect to 1000 parts by weight of the heterocyclic compound. That is, the ratio of the content of the present condensed heterocyclic compound and 4-oxo-4-[(2-phenylethyl) amino] -butyric acid is usually 100: 1 to 1: 100 by weight, preferably 10: 1 to 1:10.
  • Pests can be controlled by applying an effective amount of the pest control composition of the present invention to the plant or the soil where the plant is cultivated.
  • harmful arthropods can be controlled by applying to plant seeds and bulbs in advance.
  • the pest control composition of the present invention when the pest control composition of the present invention is applied to a plant, it is carried out by applying an effective amount of the pest control composition of the present invention to the plant and / or its cultivation place, plant seed, bulb. .
  • the pest control composition of the present invention specifically, for example, application to a foliage, flower vase or ear of a plant such as foliage spraying, application to a seedling in a nursery box, etc., before planting the plant Or application to a cultivation area and soil after planting, seed disinfection, seed soaking, application to seeds such as seed coat, application to seedlings, application to bulbs such as seed pods, and the like.
  • the plant seed means the seed of the plant in a state before being sown in the soil or the culture medium
  • the bulb is a bulb of the plant in a state before being planted in the soil or the culture medium. It means corms, tubers, rhizomes and tuberous roots.
  • Examples of the pests for which the pest control composition of the present invention is effective include harmful insects and harmful mites. Specific examples of such pests include the following.
  • Hemiptera small brown planthopper (Laodelphax striatellus), brown planthopper (Nilaparvata lugens), planthoppers such as Sejirounka (Sogatella furcifera), green rice leafhopper (Nephotettix cincticeps), Taiwan green rice leafhopper (Nephotettix virescens), tea Roh green leafhopper (Empoasca onukii) such as Leafhoppers, cotton aphids (Aphis gossypii), peach aphids (Myzus persicae), radish aphids (Brevicoryne brassicae), aphid spiraecola, tulip beetle aphids Macrosiphum euphorbiae, potato beetle aphids (Aulacorthum solani), wheat beetle aphids (Rhopalosiphum aphids), citrus a
  • Lepidoptera rice stem borer (Chilo suppressalis), Sankameiga (Tryporyza incertulas), leaf roller (Cnaphalocrocis medinalis), Watanomeiga (Notarcha derogata), Indian meal moth (Plodia interpunctella), the European corn borer (Ostrinia furnacalis), high Madara Roh moth (Hellula undalis), Common moths such as Shibatatsuga (Pediasia teterrellus), Lotus moth (Spodoptera litura), Spodoptera exigua, Ayuyotoga (Pseudaletia separata), Yotoga Mistra brasicae, Agrotis ipsilon, Tamanaginuawa (Prusia nigrisigna), Trichopulsia, Heliotis, Helicoberpa, etc.
  • Thrips of the order Thrips thrips (Franklinella occidentalis), Thrips palmi, etc.
  • Diptera seedcorn maggot (Delia platura), onion maggot (Delia antiqua) Anthomyiidae such as, rice leafminer (Agromyza oryzae), rice Hime leafminer (Hydrellia griseola), tomato leafminer, (Liriomyza sativae), legume leafminer (Liriomyza trifolii) ,
  • Leafhoppers such as Chlamatomyia horticola, leafhoppers such as Chlorops oryzae, Dacus cucurbitae, and Ceritae leafworms.
  • Coleoptera pests Western Corn Rootworm (Diabrotica virgiferavirgifera), corn rootworm such as southern corn rootworm (Diabrotica undecimpunctata howardi), cupreous chafer (Anomala cuprea), rufocuprea (Anomala rufocuprea), Scarabaeidae such as Japanese beetle (Popillia japonica) , Maizeweville (Sitophilus zeamais), Rice weevil (Lissohoptrus oryzophilus), Butter weevil (Echinocnemus squameus), Cotton weevil (Anthonomus grandis), Shiba souzo s venatus) weevils such as, Chai loco Meno mealworm (Tenebrio molitor), red flour beetle (Tribolium castaneum) Tenebrionidae such as, Inedorooimushi (Oulema oryzae), cucurbit leaf be
  • the application amount is usually 1 to 10,000 g in terms of the amount of the present condensed heterocyclic compound per 10,000 m 2 .
  • the pest control composition of the present invention is formulated into an emulsion, a wettable powder, a flowable, etc., it is usually diluted with water so that the active ingredient concentration is 0.01 to 10,000 ppm, Granules, powders, etc. are usually applied as they are.
  • preparations and water dilutions of the preparations may be sprayed directly on pests or plants such as crops to be protected from pests, and in order to control pests that inhabit cultivated soil. You may process to soil.
  • the pest control composition of the present invention can be used in cultivated land where the following “crop” is cultivated.
  • Agricultural crops corn, rice, wheat, barley, rye, oat, sorghum, cotton, soybean, peanut, buckwheat, sugar beet, rape, sunflower, sugarcane, tobacco, etc.
  • Vegetables Solanum vegetables (eggplants, tomatoes, peppers, peppers, potatoes, etc.), Cucurbitaceae vegetables (cucumbers, pumpkins, zucchini, watermelons, melons, etc.), Brassicaceae vegetables (radish, turnip, horseradish, kohlrabi, Chinese cabbage, cabbage) , Mustard, broccoli, cauliflower, etc.), asteraceae vegetables (burdock, shungiku, artichokes, lettuce, etc.), liliaceae vegetables (leek, onion, garlic, asparagus), celery family vegetables (carrot, parsley, celery, American scallop, etc.) ), Red crustacean vegetables (spinach, chard, etc.), persimmon vegetables (perilla, mint, basil, etc.), strawberry, sweet potato, yam, taro, etc.
  • Fruit trees berries (apples, pears, Japanese pears, quince, quince, etc.), nuclear fruits (peaches, plums, nectarines, ume, sweet cherry, apricot, prunes, etc.) ), Nuts (chestnut, walnut, hazel, almond, pistachio, cashew nut, macadamia nut, etc.), berries (blueberry, cranberry, blackberry, raspberry, etc.), grape, oyster, olive, loquat, banana, coffee, Date palm, coconut palm, oil palm etc.
  • Trees other than fruit trees tea, mulberry, flowering trees (Satsuki, camellia, hydrangea, sasanqua, shikimi, sakura, yurinoki, crape myrtle, eustoma, etc.), roadside trees (ash, birch, dogwood, eucalyptus, ginkgo, lilac, maple, oak) , Poplar, redwood, fu, sycamore, zelkova, blackfish, Japanese amberjack, moths, pine, pine, spruce, yew, elm, Japanese cypress, etc.), coral jug, dogwood, cedar, cypress, croton, masaki, kanamochi, etc.
  • Lawn Shiba (Nasis, Pleurotus, etc.), Bermudagrass (Neurodonidae, etc.), Bentgrass (Oleoptera, Hykonukagusa, Odonoptera, etc.), Bluegrass (Nagahagusa, Oosuzunokatabira, etc.), Fescue (Oonishi nokegusa, Drosophila, etc.) , Grass, etc.), ryegrass (rat, wheat, etc.), anemonefish, and blue whale.
  • Crop includes genetically modified crops.
  • Production Example 1 (1) A mixture of 0.76 g of N2-methyl-5-trifluoromethylpyridine-2,3-diamine, 0.50 g of 3-fluoropyridine-2-carbaldehyde, 0.50 g of sodium hydrogen sulfite and 3 ml of DMF was stirred at 120 ° C. for 8 hours. did. Saturated aqueous sodium hydrogen carbonate solution was poured into the cooled reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure.
  • Intermediate compound (M20-3) A mixture of the total amount of the obtained intermediate compound (M20-3), 1.04 g of p-toluenesulfonic acid monohydrate and 4 mL of N-methylpyrrolidinone was heated and stirred at 150 ° C. for 2.5 hours. Saturated aqueous sodium hydrogen carbonate solution was poured into the cooled reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure.
  • Production Example 6 1. 835 mg of 2- (3-ethylsulfanyl-pyridin-2-yl) -6-iodo-3-methyl-3H-imidazo [4,5-b] pyridine, 2.0 g of sodium pentafluoropropionate, copper iodide A mixture of 0 g, NMP 10 mL, and xylene 50 mL was heated and stirred at 150 ° C. for 8 hours. After cooling to room temperature, a 40% aqueous ammonia solution and a saturated aqueous sodium hydrogen carbonate solution were added, and the mixture was extracted with ethyl acetate. The organic layer was dried over sodium sulfate and concentrated under reduced pressure.
  • Production Example 9 (2) A mixture of intermediate compound (M20-7) 3.4 g, p-toluenesulfonic acid monohydrate 5.8 g, DMF 30 mL, toluene 120 mL was heated and stirred at 130 ° C. for 12 hours. After allowing to cool to room temperature, saturated aqueous sodium hydrogen carbonate solution was added, and the mixture was extracted with ethyl acetate. The organic layer was dried over sodium sulfate and concentrated under reduced pressure.
  • intermediate compound (M20-7) 3.4 g, p-toluenesulfonic acid monohydrate 5.8 g, DMF 30 mL, toluene 120 mL was heated and stirred at 130 ° C. for 12 hours. After allowing to cool to room temperature, saturated aqueous sodium hydrogen carbonate solution was added, and the mixture was extracted with ethyl acetate. The organic layer was dried over sodium sulfate and concentrated under reduced pressure.
  • Intermediate compound (M20-9) A mixture of the total amount of the obtained intermediate compound (M20-9), 1.04 g of p-toluenesulfonic acid monohydrate and 3.5 mL of N-methylpyrrolidinone was heated and stirred at 150 ° C. for 2 hours. Saturated aqueous sodium hydrogen carbonate solution was poured into the cooled reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure.
  • Production Example 12 (2) A mixture of 0.45 g of the intermediate compound (M20-11), 0.70 g of p-toluenesulfonic acid monohydrate and 4 mL of NMP was stirred at 150 ° C. for 2 hours. Saturated aqueous sodium hydrogen carbonate solution was poured into the cooled reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure.
  • Production Example 12 (3) Intermediate compound instead of 2- (3-fluoropyridin-2-yl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine (intermediate compound (M6-2)) (M6-11) and 2- (3-ethylsulfanyl-2-yl) -6- (trifluoromethyl) thiazolo [5,4-b] pyridine according to the method described in Production Example 1 (2) (Hereinafter may be referred to as the present condensed heterocyclic compound 41).
  • This condensed heterocyclic compound 12 1 H-NMR (CDCl 3 ) ⁇ : 8.98-8.93 (2H, m), 8.66 (1H, dd), 8.57 (1H, d), 7.69 (1H, dd), 4.13 (2H, q), 1.45 (3H, t).
  • the present condensed heterocyclic compound 22 1 H-NMR (CDCl 3 ) ⁇ : 8.96 (1H, dd), 8.68 (1H, dd), 8.62 (1H, s), 8.20 (1H, s), 7.74 ( 1H, dd), 4.06 (2H, q), 1.44 (3H, t).
  • Production Example 13 (2) A mixture of 710 mg of the intermediate compound (P9′-1) and 12 mL of DMF was cooled to ⁇ 60 ° C., and 10 g of trifluoroiodomethane was added. To this mixture, 1.2 mL of tetrakis (dimethylamino) ethylene was added dropwise at -40 ° C. It heated up to -10 degreeC and stirred at -10 degreeC for 5 hours. Water was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was dried over sodium sulfate and concentrated under reduced pressure.
  • the present condensed heterocyclic compound 14 1 H-NMR (CDCl 3 ) ⁇ : 8.87-8.83 (1H, m), 8.73-8.64 (2H, m), 8.41 (1H, d), 7.72-7 .66 (1H, m), 4.34 (3H, s), 3.72-3.62 (1H, m), 3.17-3.05 (1H, m), 1.47 (3H, t ).
  • the residue was subjected to silica gel column chromatography to give 2- (3-ethylsulfonyl-pyridin-2-yl) -3-methyl-6-trifluoromethylsulfonyl-3H-imidazo [4,5-b] pyridine (hereinafter, This may be referred to as the present condensed heterocyclic compound 16.) 280 mg was obtained.
  • the present condensed heterocyclic compound 16 1 H-NMR (CDCl 3 ) ⁇ : 9.08 (1H, d), 9.04 (1H, dd), 8.71 (1H, d), 8.57 (1H, dd), 7.79 ( 1H, dd), 3.93 (3H, s), 3.82 (2H, q), 1.38 (3H, t).
  • Production Example 17 (1) A mixture of 590 mg N2-methyl-5-pentafluoroethyl-pyridine-2,3-diamine, 560 mg 3-chloro-5-trifluoromethyl-pyridine-2-carboxylic acid, 520 mg EDCI hydrochloride, 35 mg HOBt, 5 mL pyridine, Stir at room temperature for 5 hours. Water was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was dried over sodium sulfate and concentrated under reduced pressure to obtain an intermediate compound (M20-17).
  • Intermediate compound (M20-17) The obtained intermediate compound (M20-17) was dissolved in a mixed solvent of 7.5 mL of DMF and 30 mL of toluene, 1.5 g of p-toluenesulfonic acid monohydrate was added, and the mixture was stirred at 160 ° C. for 6 hours. The reaction mixture was allowed to cool to room temperature, saturated aqueous sodium hydrogen carbonate solution was added, and the mixture was extracted with t-butyl methyl ether. The organic layer was dried over sodium sulfate and concentrated under reduced pressure.
  • Production Example 17 (2) Instead of 2- (3-fluoropyridin-2-yl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine (intermediate compound (M6-2)), an intermediate Using compound (M6-17), 2- (3-ethylsulfanyl-5-trifluoromethyl-pyridin-2-yl) -3-methyl-6-penta according to the method described in Production Example 1 (2) Fluoroethyl-3H-imidazo [4,5-b] pyridine (hereinafter sometimes referred to as the present condensed heterocyclic compound 17) was obtained.
  • the present condensed heterocyclic compound 18 1 H-NMR (CDCl 3 ) ⁇ : 9.10 (1H, d), 8.94 (1H, d), 8.76 (1H, d), 8.36 (1H, d), 4.41 ( 3H, s), 3.76-3.66 (1H, m), 3.18-3.07 (1H, m), 1.49 (3H, t).
  • the present condensed heterocyclic compound 19 1 H-NMR (CDCl 3 ) ⁇ : 9.27 (1H, d), 8.80 (1H, d), 8.76 (1H, s), 8.34 (1H, s), 4.01- 3.94 (5H, m), 1.41 (3H, t).
  • the residue was subjected to silica gel column chromatography to give 2- (3-ethylsulfonyl-pyridin-2-yl) -3-methyl-6-trifluoromethylsulfinyl-3H-imidazo [4,5-b] pyridine (hereinafter, This may be referred to as the present condensed heterocyclic compound 20.) 353 mg was obtained.
  • the present condensed heterocyclic compound 20 1 H-NMR (CDCl 3 ) ⁇ : 9.02 (1H, dd), 8.77 (1H, d), 8.60-8.52 (2H, m), 7.75 (1H, dd), 3.91 (3H, s), 3.83 (2H, q), 1.38 (3H, t).
  • Production Example 22 (1) A mixture of 5.2 g of 4-aminophenylsulfur pentafluoride, 2.7 mL of acetic anhydride, 6.6 mL of triethylamine and 20 mL of chloroform was stirred at room temperature for 3 hours. Water was poured into the reaction mixture, and the mixture was extracted with chloroform. The obtained residue was recrystallized using hexane and ethyl acetate to obtain 5.4 g of 4-acetamidophenylsulfur pentafluoride.
  • Production Example 22 (4) Instead of (4-iodo-2-nitro-phenyl) -methyl-amine, methyl- (2-nitro-4-pentafluorosulfanyl-phenyl) -amine was used, and the method described in Production Example 21 (2) was used. Accordingly, N1-methyl-4-pentafluorosulfanyl-benzene-1,2-diamine was obtained.
  • the present condensed heterocyclic compound 24 1 H-NMR (CDCl 3 ) ⁇ : 8.96 (1H, dd), 8.50 (1H, dd), 8.24 (1H, d), 7.79 (1H, dd), 7.68 ( 1H, dd), 7.48 (1H, d), 3.82 (2H, q), 3.75 (3H, s), 1.34 (3H, t).
  • the present condensed heterocyclic compound 42 1 H-NMR (CDCl 3 ) ⁇ : 8.73 (1H, s), 8.65 (1H, d), 8.49 (1H, d), 7.91 (1H, s), 4.04 ( 3H, s), 3.01 (2H, q), 1.39 (3H, t).
  • the present condensed heterocyclic compound 28 1 H-NMR (CDCl 3 ) ⁇ : 8.75 (1H, d), 8.71 (1H, d), 8.50 (1H, d), 7.93 (1H, d), 4.10 ( 3H, s), 3.03 (2H, q), 1.41 (3H, t).
  • the obtained residue was subjected to silica gel column chromatography to give 2- (3-ethylsulfonyl-5-trifluoromethyl-pyridin-2-yl) -3-methyl-6-trifluoromethylsulfanyl-3H-imidazo [4 , 5-b] pyridine (hereinafter sometimes referred to as the present condensed heterocyclic compound 44) 0.24 g was obtained.
  • the present condensed heterocyclic compound 44 1 H-NMR (CDCl 3 ) ⁇ : 9.24 (1H, d), 8.79 (1H, d), 8.74 (1H, d), 8.40 (1H, d), 3.97 ( 2H, q), 3.93 (3H, s), 1.42 (3H, t).
  • the residue was subjected to silica gel column chromatography to give 2- (3-ethylsulfanyl-pyridin-2-yl) -1-methyl-5-pentafluoroethyl-1H-benzimidazole (hereinafter referred to as the present condensed heterocyclic compound 26). In some cases) 240 mg was obtained.
  • the present condensed heterocyclic compound 26 1 H-NMR (CDCl 3 ) ⁇ : 8.50 (1H, dd), 8.16 (1H, s), 7.77 (1H, dd), 7.57 (1H, d), 7.53 ( 1H, d), 7.36 (1H, dd), 3.93 (3H, s), 2.94 (2H, q), 1.33 (3H, t).
  • Production Example 28 (2) A mixture of 800 mg of the intermediate compound (M20-29), 350 mg of sodium ethanethiolate and 10 mL of DMF was stirred at 100 ° C. for 5 hours. Saturated aqueous sodium hydrogen carbonate solution was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was dried over sodium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to give 2- (3-ethylsulfanyl-pyridin-2-yl) -1-methyl-5-trifluoromethyl-1H-benzimidazole (hereinafter referred to as the present condensed heterocyclic compound 30). 410 mg was obtained.
  • the present condensed heterocyclic compound 32 1 H-NMR (CDCl 3 ) ⁇ : 8.95 (1H, dd), 8.50 (1H, dd), 8.09 (1H, d), 7.66 (1H, dd), 7.61 ( 1H, d), 7.53 (1H, d), 3.83 (2H, q), 3.75 (3H, s), 1.33 (3H, t).
  • the present condensed heterocyclic compound 34 1 H-NMR (CDCl 3 ) ⁇ : 9.05 (1H, d), 8.91 (1H, d), 8.12 (1H, d), 7.67 (1H, dd), 7.60 ( 1H, d), 4.32 (3H, s), 3.80-3.70 (1H, m), 3.15-3.05 (1H, m), 1.51 (3H, t).
  • the present condensed heterocyclic compound 36 1 H-NMR (CDCl 3 ) ⁇ : 8.79 (1H, d), 8.54 (1H, dd), 8.33 (1H, d), 7.99 (1H, dd), 7.69 ( 1H, dd), 3.85-3.74 (4H, m), 3.52-3.42 (1H, m), 1.34 (3H, t).
  • the present condensed heterocyclic compound 37 1 H-NMR (CDCl 3 ) ⁇ : 9.03 (1H, dd), 8.53 (1H, dd), 8.47 (1H, d), 7.92 (1H, d), 7.77 ( 1H, dd), 4.29 (3H, s), 3.69 (2H, q), 1.36 (3H, t).
  • the present condensed heterocyclic compound 38 1 H-NMR (CDCl 3 ) ⁇ : 8.72 (1H, d), 8.20 (1H, s), 7.91 (1H, d), 7.60 (1H, d), 7.55 ( 1H, d), 4.00 (3H, s), 3.01 (2H, q), 1.39 (3H, t).
  • the present condensed heterocyclic compound 40 2- (3-ethylsulfonyl-5-trifluoromethyl-pyridin-2-yl) -1-methyl-5-pentafluoroethyl-1H-benzimidazole (hereinafter referred to as the present condensed heterocyclic compound 40).
  • the present condensed heterocyclic compound 39 1 H-NMR (CDCl 3 ) ⁇ : 9.05 (1H, d), 8.91 (1H, d), 8.10 (1H, s), 7.66-7.60 (2H, m), 4.33 (3H, s), 3.80-3.69 (1H, m), 3.17-3.07 (1H, m), 1.50 (3H, t).
  • the present condensed heterocyclic compound 40 1 H-NMR (CDCl 3 ) ⁇ : 9.22 (1H, d), 8.77 (1H, d), 8.08 (1H, s), 7.63 (1H, d), 7.58 ( 1H, d), 3.99 (2H, q), 3.84 (3H, s), 1.40 (3H, t).
  • the present condensed heterocyclic compound 46 1 H-NMR (CDCl 3 ) ⁇ : 8.99 (1H, dd), 8.51 (1H, dd), 8.00 (1H, d), 7.75 (1H, d), 7.72 ( 1H, dd), 4.03 (3H, s), 3.73 (2H, q), 1.33 (3H, t).
  • the present condensed heterocyclic compound 48 1 H-NMR (CDCl 3 ) ⁇ : 9.27 (1H, d), 8.76 (1H, d), 8.49 (1H, d), 7.94 (1H, d), 4.33 ( 3H, s), 3.80 (2H, q), 1.40 (3H, t).
  • This condensed heterocyclic compound 51 1 H-NMR (CDCl 3 ) ⁇ : 8.75 (1H, s), 8.50 (1H, s), 8.12 (1H, s), 7.94 (1H, s), 4.28 ( 3H, s), 3.75-3.65 (1H, m), 3.55-3.44 (1H, m), 1.38 (3H, t).
  • Production Example 43 (1) 2.60 g of 2-chloro-3-nitro-5-trifluoromethylpyridine, 0.79 g of 2,2,2-trifluoroethylamine, 1.04 g of N, N-diisopropylethylamine and 5 ml of N-methyl-2-pyrrolidone The mixture was stirred at room temperature for 10 hours. A 10% aqueous citric acid solution was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over sodium sulfate, and concentrated under reduced pressure to obtain 1.83 g of (3-nitro-5-trifluoromethylpyridin-2-yl)-(2,2,2-trifluoroethyl) amine.
  • Production Example 44 A mixture of 0.89 g of the intermediate compound (M3-44), 1.14 g of p-toluenesulfonic acid monohydrate, 10 ml of N-methyl-2-pyrrolidone and 10 ml of xylene was dehydrated using a Dean-Stark apparatus. The mixture was heated to reflux for 8 hours. The reaction mixture was allowed to cool, water was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over sodium sulfate, and concentrated under reduced pressure.
  • Production Example 47 (1) A mixture of 20.0 g of 2-chloro-5-iodopyridine, 77.8 g of sodium pentafluoropropionate, 31.8 g of copper (I) iodide, 84 ml of xylene and 84 ml of N-methylpyrrolidone was heated to 160 ° C. and heated. The mixture was stirred for 6 hours under reflux. The reaction mixture was cooled to room temperature, water was added, and the mixture was extracted with methyl-tert-butyl ether. The organic layer was dried over sodium sulfate and then concentrated under reduced pressure to obtain 2-chloro-5-pentafluoroethylpyridine.
  • Production Example 47 (2) Half amount of 2-chloro-5-pentafluoroethylpyridine obtained in Production Example 47 (1), 14.4 g of zinc (II) cyanide, 2.42 g of tetrakistriphenylphosphine palladium and 84 ml of N-methylpyrrolidone The mixture was heated to 80 ° C. and stirred with heating for 2.5 hours. After the reaction mixture was cooled to room temperature, water and methyl-tert-butyl ether were added, the precipitate was filtered through Celite (registered trademark), and the residue was washed with methyl-tert-butyl ether.
  • Celite registered trademark
  • Production Example 47 (4) A mixture of 5.5 ml of tetramethylpiperidine and 58 ml of THF was cooled to ⁇ 78 ° C., 1.6 M n-butyllithium hexane solution was added dropwise, and the mixture was warmed to room temperature and stirred for 10 minutes. The mixture was cooled again to ⁇ 78 ° C., a THF solution of 3.52 g of 5-pentafluoropyridine-2-carboxylic acid was added dropwise, and the mixture was stirred at ⁇ 78 ° C. for 1 hour. After dropwise addition of 4.0 ml of diethyl disulfide at ⁇ 78 ° C., the mixture was warmed to room temperature and stirred for 1 hour.
  • intermediate compound (M3-45) 1 H-NMR (CDCl 3 ) ⁇ : 9.57 (1H, brs), 8.54-8.52 (1H, m), 8.37-8.35 (1H, m), 7.94-7 .92 (1H, m), 7.89-7.87 (1H, m), 4.97 (1H, brs), 3.08 (3H, d), 2.99 (2H, q), 1. 45 (3H, t)
  • a mixture of the total amount of the obtained intermediate compound (M3-45) and 5 ml of acetic acid was heated to 120 ° C. and stirred for 3 hours while heating under reflux. After cooling to room temperature, the mixture was concentrated under reduced pressure.
  • the present condensed heterocyclic compound 72 1 H-NMR (CDCl 3 ) ⁇ : 9.21-9.19 (1H, m), 8.81-8.79 (1H, m), 8.76-8.75 (1H, m), 8 .35-8.33 (1H, m), 3.99-3.93 (5H, m), 1.41 (3H, t)
  • Intermediate compound (M3-46) 1 H-NMR (CDCl 3 ) ⁇ : 9.59 (1H, brs), 8.54-8.52 (1H, m), 8.32-8.30 (1H, m), 7.89-7 .87 (1H, m), 7.85-7.83 (1H, m), 5.04 (1H, brs), 3.09 (3H, d), 2.99 (2H, q), 1. 45 (3H, t)
  • a mixture of the total amount of the obtained intermediate compound (M3-46) and 4 ml of acetic acid was heated to 120 ° C. and stirred for 3 hours while heating under reflux. After cooling to room temperature, the mixture was concentrated under reduced pressure.
  • the crude product was subjected to silica gel column chromatography to give 2- (3-ethylsulfonyl-5-pentafluoroethylpyridin-2-yl) -3-methyl-6-pentafluoroethyl-3H-imidazo [4,5- b] 0.34 g of pyridine (hereinafter sometimes referred to as the present condensed heterocyclic compound 74) was obtained.
  • the present condensed heterocyclic compound 74 1 H-NMR (CDCl 3 ) ⁇ : 9.21-9.20 (1H, m), 8.77-8.74 (2H, m), 8.32-8.31 (1H, m), 4 .00-3.94 (5H, m), 1.41 (3H, t)
  • This condensed heterocyclic compound 404 1 H-NMR (CDCl 3 ) ⁇ : 9.08-8.97 (1H, m), 8.58-8.46 (1H, m), 8.41-8.26 (2H, m), 7 84-7.70 (1H, m), 4.12 (3H, s), 3.72-3.59 (2H, m), 3.33 (3H, s), 1.39-1.22 (3H, m).
  • Production Example 68 (1) A mixture of 1.0 g 2-amino-4- (trifluoromethylsulfanyl) phenol, 0.87 g 3-ethylsulfanylpicolinic acid, 1.10 g EDCI hydrochloride and 10 ml chloroform was stirred at room temperature for 30 minutes. Water was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure.
  • This condensed heterocyclic compound 443 1 H-NMR (CDCl 3 ) ⁇ : 9.03 (1H, dd), 8.60 (1H, dd), 8.19 (1H, d), 7.80-7.71 (3H, m), 4.02 (2H, q), 1.43 (3H, t).
  • the obtained residue is subjected to silica gel column chromatography, and may be referred to as 2- (3-ethylsulfonylpyridin-2-yl) -5- (trifluoromethylsulfonyl) benzoxazole (hereinafter referred to as the present condensed heterocyclic compound 445).
  • the present condensed heterocyclic compound 445 1 H-NMR (CDCl 3 ) ⁇ : 9.05 (1H, dd), 8.61 (1H, dd), 8.59 (1H, d), 8.17 (1H, dd), 7.96 ( 1H, d), 7.80 (1H, dd), 3.98 (2H, q), 1.45 (3H, t).
  • Production Example 71 A mixture of 1.0 g of 2-amino-4- (trifluoromethylsulfanyl) phenol, 1.08 g of 3-chloro-5-trifluoromethylpicolinic acid, 1.10 g of EDCI hydrochloride and 10 ml of chloroform was stirred at room temperature for 1 hour. did. Water was poured into the reaction mixture, and the mixture was extracted with ethyl acetate.
  • the obtained residue was subjected to silica gel column chromatography to give 2- (3-ethylsulfanyl-5-trifluoromethylpyridin-2-yl) -5- (trifluoromethylsulfanyl) benzoxazole (hereinafter referred to as the present condensed heterocyclic ring). 1.31 g) was obtained.
  • the present condensed heterocyclic compound 451 1 H-NMR (CDCl 3 ) ⁇ : 8.78 (1H, d), 8.30 (1H, s), 7.94 (1H, d), 7.77-7.75 (2H, m), 3.11 (2H, q), 1.51 (3H, t).
  • This condensed heterocyclic compound 453 1 H-NMR (CDCl 3 ) ⁇ : 9.25 (1H, d), 8.84 (1 H, d), 8.22 (1 H, d), 7.82 (1 H, dd), 7.77 ( 1H, d), 4.11 (2H, q), 1.47 (3H, t).
  • the present condensed heterocyclic compound 454 1 H-NMR (CDCl 3 ) ⁇ : 9.27 (1H, d), 8.85 (1H, d), 8.39 (1H, s), 7.96 (1H, d), 7.92 ( 1H, d), 4.09 (2H, q), 1.48 (3H, t).
  • Production Example 75 (1) A mixture of 27 ml of tert-butanol and 3.15 g of potassium hydroxide was stirred with heating under reflux for 1 hour, 6.0 g of 2-chloro-5-trifluoromethylsulfanylpyridine and 3 mL of tert-butanol were added with a dropping funnel, and the mixture was heated under reflux. Stir for 5 hours. The reaction mixture was allowed to cool to room temperature, concentrated hydrochloric acid was added, the solid was filtered and washed with ethanol.
  • Production Example 75 (3) A mixture of 4.6 g of iron powder, 0.5 mL of acetic acid, 20 mL of ethanol and 15 mL of water was stirred at 70 ° C., and 2 g of 2-hydroxy-3-nitro-5-trifluoromethylsulfinylpyridine was added thereto. Stir for hours. The reaction mixture was allowed to cool to room temperature and filtered through Celite (registered trademark). The obtained filtrate was concentrated under reduced pressure, saturated aqueous sodium hydrogen carbonate solution was added, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure.
  • Production Example 75 (4) A mixture of 0.63 g of 3-amino-2-hydroxy-5-trifluoromethylsulfinylpyridine, 0.55 g of 3-ethylsulfanylpicolinic acid, 0.68 g of EDCI hydrochloride and 20 ml of pyridine was stirred at room temperature for 3 hours. Water was added to the reaction mixture, and the mixture was stirred at room temperature for 30 minutes. The precipitated solid was collected by filtration and dried under reduced pressure to obtain 0.73 g of 3-ethylsulfanyl-N- [2-hydroxy-5-trifluoromethylsulfinylpyridin-3-yl] picolinamide.
  • Production Example 78 (1) A mixture of 0.67 g 3-amino-2-hydroxy-5-trifluoromethylsulfinylpyridine, 0.75 g 3-ethylsulfanyl-5-trifluoromethylpicolinic acid, 0.68 g EDCI hydrochloride and 20 ml pyridine is stirred at room temperature. Stir for 1.5 hours. Water was added to the reaction mixture, and the mixture was stirred at room temperature for 30 minutes. The precipitated solid was collected by filtration and dried under reduced pressure to give 1.28 g of 3-ethylsulfanyl-5-trifluoromethyl-N- [2-hydroxy-5-trifluoromethylsulfinylpyridin-3-yl] picolinamide. Got.
  • the obtained residue was subjected to silica gel column chromatography to give 2- (3-ethylsulfanyl-5-trifluoromethylpyridin-2-yl) -6- (trifluoromethylsulfinyl) oxazolo [5,4-b] pyridine. 0.94 g was obtained (hereinafter may be referred to as the present condensed heterocyclic compound 478).
  • the present condensed heterocyclic compound 478 1 H-NMR (CDCl 3 ) ⁇ : 8.83 (1H, d), 8.81 (1H, d), 8.75 (1H, d), 7.97 (1H, d), 3.13 ( 2H, q), 1.51 (3H, t).
  • the obtained residue was subjected to silica gel column chromatography to give 2- (3-ethylsulfonyl-5-trifluoromethylpyridin-2-yl) -6- (trifluoromethylsulfonyl) oxazolo [5,4-b] pyridine. 0.21 g was obtained (hereinafter may be referred to as the present condensed heterocyclic compound 450).
  • the present condensed heterocyclic compound 450 1 H-NMR (CDCl 3 ) ⁇ : 9.32 (1H, d), 9.17 (1H, d), 8.85-8.82 (2H, m), 3.95 (2H, q), 1.50 (3H, t).
  • the condensed heterocyclic compound 456) and 2- (3-ethylsulfonyl-1-oxy-pyridin-2-yl) -6- (trifluoromethylsulfonyl) oxazolo [5,4-b] pyridine ( Hereinafter, this condensed heterocyclic compound 458 may be referred to).
  • the present condensed heterocyclic compound 456 The present condensed heterocyclic compound 458
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , A 1 , A 2 , and n represent the combinations described in the following [Table 1] to [Table 20].
  • the present condensed heterocyclic compound 36 is the present condensed heterocyclic compound 36
  • the present condensed heterocyclic compound 48 is the present condensed heterocyclic compound 48
  • the present condensed heterocyclic compound 400 is the present condensed heterocyclic compound 400
  • the present condensed heterocyclic compound 456 is the present condensed heterocyclic compound 456
  • Me represents a methyl group
  • Et represents an ethyl group
  • Pr represents a propyl group
  • Bu represents a butyl group
  • tBu represents a tertiary butyl group
  • IPr represents an isopropyl group
  • CycPr represents a cyclopropyl group.
  • Formulation Example 1 1 part of the present condensed heterocyclic compounds 1 to 481, 5 parts, 10 parts of 4-oxo-4-[(2-phenylethyl) amino] -butyric acid (hereinafter referred to as Compound I), white carbon and polyoxy
  • Compound I 4-oxo-4-[(2-phenylethyl) amino] -butyric acid
  • white carbon and polyoxy Each preparation is obtained by mixing 35 parts of a mixture with an ethylene alkyl ether sulfate ammonium salt (weight ratio 1: 1) and water to make a total amount of 100 parts and finely pulverizing by a wet pulverization method.
  • Formulation Example 2 After mixing 10 parts of the present condensed heterocyclic compounds 1 to 481, 2 parts of Compound I, 1.5 parts of sorbitan trioleate, and 28 parts of an aqueous solution containing 2 parts of polyvinyl alcohol, and then finely pulverizing them by a wet pulverization method. Into this, an aqueous solution containing 0.05 part of xanthan gum and 0.1 part of aluminum magnesium silicate is added to make a total amount of 90 parts, and further 10 parts of propylene glycol is added and stirred and mixed to obtain each preparation.
  • Test example 1 This condensed heterocyclic compound 3, 4, 5, 9, 15, 16, 17, 18, 19, 20, 22, 25, 27, 28, 29, 34, 36, 39, 48, 50, 53, 71, 72 , 74, 81, 85, 89, 99, 130, 312, 399, 404, 409, 414, 419, 421, 423, 443, 444, 445, 464 and 467, respectively, and the volume ratio is 4: 4, respectively.
  • a test drug solution was prepared by mixing a water diluted solution of the present condensed heterocyclic compound and a water diluted solution of Compound I.
  • Cabbage (Brassicae oleracea) leaf disc (1.5 cm in diameter) was accommodated in each well of a 24-well microplate (manufactured by Becton Dickinson) and sprayed with 40 ⁇ L of the test drug solution per well.
  • the pest control composition of the present invention can be used to control pests.

Abstract

La présente invention concerne une composition anti-animaux nuisibles contenant les composés suivants : un composé pouvant être représenté par la formule (1) ou un N-oxyde d'un tel composé; et de l'acide 4-oxo-4-[(2-phényléthyl)amino]-butyrique. La présente invention concerne un procédé de lutte contre les animaux nuisibles comportant une étape consistant à appliquer une quantité efficace de la composition anti-animaux nuisibles susmentionnée sur des plantes, des semences végétales, des bulbes ou le sol dans lequel sont cultivées des plantes. Ladite composition anti-animaux nuisibles et ledit procédé de lutte contre les animaux nuisibles présentent une remarquable efficacité en matière de lutte contre les animaux nuisibles.
PCT/JP2014/052178 2013-01-31 2014-01-24 Composition et procédé permettant de lutter contre les animaux nuisibles WO2014119699A1 (fr)

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CN201480006602.6A CN104955333A (zh) 2013-01-31 2014-01-24 有害生物防除组合物和有害生物的防除方法
EP14745632.1A EP2962565A1 (fr) 2013-01-31 2014-01-24 Composition et procédé permettant de lutter contre les animaux nuisibles
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WO2020216695A1 (fr) 2019-04-23 2020-10-29 Bayer Aktiengesellschaft Procédés et compositions pour la lutte contre les insectes dans des plantes cultivées
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US10927106B2 (en) 2016-10-12 2021-02-23 Pharmasum Therapeutics As Benzothiazole derivatives as DYRK1 inhibitors
WO2019138018A1 (fr) 2018-01-15 2019-07-18 Syngenta Participations Ag Dérivés hétérocycliques à activité pesticide comportant des substituants contenant du soufre
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WO2021009311A1 (fr) 2019-07-17 2021-01-21 Syngenta Crop Protection Ag Dérivés hétérocycliques à action pesticide comprenant des substituants contenant du soufre
CN112824402A (zh) * 2019-11-21 2021-05-21 浙江省化工研究院有限公司 一类苯并咪唑类衍生物、其制备方法及应用
CN112824402B (zh) * 2019-11-21 2023-02-28 浙江省化工研究院有限公司 一类苯并咪唑类衍生物、其制备方法及应用

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